Photoactive catalyst compositions

ABSTRACT

The present disclosure is directed to photosensitive compositions ‘Fischer-type’ ruthenium carbene catalysts containing chelated 2,2′-bipyridine ligands and methods of using the same. These catalysts are surprisingly active even when using relatively low intensity diode light sources. The 2,2′-bipyridine-chelated ruthenium photocatalysts show reactivity at substantially lower exposure levels than other photoactive chelating dinitrogen ligands of similar structure. The present disclosure is further directed to novel photosensitive compositions, their use as photoresists, and methods related to patterning polymer layers on substrates.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority to U.S. PatentApplication Ser. No. 62/383,146, filed Sep. 2, 2016, the contents ofwhich are each incorporated by reference in their entirety for any andall purposes.

GOVERNMENT RIGHTS

This invention was made with government support under Grant No. 16447467awarded by the National Science Foundation and Grant No.DE-AC05-060R23100 awarded by the US Department of Energy. The governmenthas certain rights in the invention.

TECHNICAL FIELD

The present disclosure relates to functionalized photolithographiccompositions. It also relates to metathesis reactions catalyzed byorganometallic coordination compounds, particularly by Fischer-typeruthenium carbene catalysts, and in particular those containingchelating 2,2′-bipyridine ligands.

BACKGROUND

Photolithography is the patterning technique at the foundation ofmicrofabrication, the core of modern integrated circuit technology. In aphotoresist, the pattern of optical irradiation is converted to apattern of chemically distinct regions, typically through photoinitiatedfunctional group cleavage or crosslinking. Many modern photoresistsemploy the concept of “chemical amplification,” in which aphotogenerated catalyst reacts with many sites. For example, photoacidgenerators are commonly employed in chemically amplified resists, eitherto catalyze a ring opening polymerization or initiate a cascade ofdeprotective bond scissions within a polymer matrix, imparting newsolubility properties to the irradiated regions. While there are anumber of light-mediated reactions that could be, in principle, employedin photolithography, very few have been implemented. Despite the factthat there are hundreds of commercially available photoresists, thefunctional diversity amongst these materials is severely limited. Inmost applications, the photoresist serves the sole purpose of asacrificial mask or mold; very rarely is the resist materialincorporated as a structural element or chemically functional interface.The ability to generate new kinds of chemically functional materialsdirectly via photolithography would enable a host of new applications,for example in microelectromechanical systems (MEMS), microfluidics,patterned biomaterials and artificial optical materials. Olefinmetathesis is a robust synthetic methodology that has led to newpolymeric materials with many applications, such as drug delivery,organic electronics, and photonic crystals.

SUMMARY

Certain embodiments provide photosensitive compositions, eachcomposition comprising a ruthenium carbene metathesis catalyst ofFormula (I) or a geometric isomer thereof:

admixed within a polymerizable material matrix comprising at least oneunsaturated organic precursor, including ROMP or cross-metathesisprecursors;

wherein

X¹ and X² are independent anionic ligands;

Y is O, N—R¹, or S, preferably O; and

Q is a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or—CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, andR¹⁴ are independently hydrogen, optionally substituted hydrocarbyl,optionally substituted heteroatom-containing hydrocarbyl, or afunctional group;

R¹ and R² are independently hydrogen, optionally substitutedhydrocarbyl, optionally substituted heteroatom-containing hydrocarbyl,or may be linked together to form an optionally substituted cyclicaliphatic group;

R³ and R⁴ are independently optionally substituted hydrocarbyl,preferably an optionally substituted adamantyl or substituted phenyl;and

R⁵ and R⁶ are independently H or electron-withdrawing orelectron-donating groups, including C₁₋₂₄alkyl, C₁₋₂₄alkoxy,C₁₋₂₄fluoroalkyl (including perfluoroalkyl), C₁₋₂₄fluoroalkoxy(including perfluoroalkoxy), C₁₋₂₄alkylhydroxy, C₁₋₂₄alkoxyhydroxy,C₁₋₂₄fluoroalkylhydroxy(including perfluoroalkylhydroxy),C₁₋₂₄fluoroalkoxyhydroxy (including perfluoroalkoxyhydroxy) halo (e.g.,F, Cl, Br), cyano, nitro, or hydroxyl, silyl, or phosphonyl; and

m and n are independently 1, 2, 3, or 4.

R⁵ and R⁶ can also independently be optionally substituted aryl,alkaryl, aralkyl, aryloxy, alkaryloxy, aralkoxy, primary amine,secondary amine, tertiary amine, amido, alkylcarbonyl, alkoxycarbonyl,or aminocarbonyl

In some of these compositions one or both of R⁵ and R⁶ is H. In some ofthese compositions m=n=1. In some of these compositions one or both ofR⁵ and R⁶ is C₁₋₁₂alkyl, C₁₋₁₂fluoroalkyl (including perfluoroalkyl),C₁₋₁₂fluoroalkoxy (including perfluoroalkoxy), C₁₋₁₂alkylhydroxy,C₁₋₁₂alkoxyhydroxy, C₁₋₁₂fluoroalkylhydroxy(includingperfluoroalkylhydroxy), C₁₋₁₂fluoroalkoxyhydroxy (includingperfluoroalkoxyhydroxy), F, Cl, Br, or hydroxy. In some embodiments, R⁵and R⁶ are present in the 3,3′ or 4,4′ or 5,5′ or 6,6′ position,respectively

In related embodiments, the metathesis catalyst comprises a compoundhaving a structure of IA, or a geometric isomer thereof:

The bipyridinyl ruthenium metathesis catalysts of Formula (I) may beadded as-described or generated in-situ.

In other specific embodiments, the metathesis catalyst of thephotosensitive composition, upon activation by irradiation of light ofat at least one wavelength in a range of from about 250 nm to about 800nm, can crosslink or polymerize at least one of the unsaturated organicprecursors.

Other embodiments provide methods of patterning polymeric image on asubstrate, each method comprising; (a) depositing a layer of one of theinventive photosensitive compositions on a substrate; (b) irradiating aportion of the layer of photosensitive composition with a lightcomprising at at least one wavelength in a range of from about 250 nm toabout 800 nm, or a sub-range therewithin, so as to polymerize theirradiated portion of the layer, thereby providing polymerized andunpolymerized nor non-irradiated regions in the layer. In otherembodiments, the methods further comprise removing the unpolymerizedregion of the pattern.

Still other embodiments provide photosensitive compositions, eachfurther comprising and organometallic moiety having at least one alkeneor one alkyne bond capable of metathesizing with the at least oneunsaturated organic precursor. In some of these embodiments, theorganometallic moiety comprises a Group 3 to Group 12 transition metal,preferably Fe, Co, Ni, Ti, Al, Cu, Zn, Ru, Rh, Ag, Ir, Pt, Au, or Hg,which may be capable of catalyzing a variety of organic and inorganicreactions.

Other embodiments provide photosensitive compositions, each alsocomprising any one or more of the more general range of bipyridinylruthenium metathesis catalyst admixed or dissolved within apolymerizable material matrix comprising at least one unsaturatedorganic precursor, each organic precursor having at least one alkene orone alkyne bond; where the at least one unsaturated organic precursorcomprises a compound having a structure:

wherein

Z is —O— or C(R_(a))(R_(b));

R^(P) is independently H; or C₁₋₆ alkyl optionally substituted at thedistal terminus with —N(R_(a))(R_(b)), —O—R_(a), —C(O)O—R_(a),—OC(O)—(C₁₋₆ alkyl), or —OC(O)—(C₆₋₁₀ aryl); or an optionally protectedsequence of 3 to 10 amino acids (preferably including R-G-D orarginine-glycine-aspartic acid);

W is independently —N(R_(a))(R_(b)), —O—R_(a), or —C(O)O—R_(a),—P(O)(OR_(a))₂, —SO₂(OR_(a)), or SO₃—;

R_(a) and R_(b) are independently H or C₁₋₆ alkyl;

the C₆₋₁₀ aryl is optionally substituted with 1, 2, 3, 4, or 5optionally protected hydroxyl groups (the protected hydroxyl groupspreferably being benzyl); and

n is independently 1, 2, 3, 4, 5, or 6.

In some embodiments, the unsaturated organic precursor may be mono- orpoly-functionalized

The methods of using these photosensitive composition may comprise: (a)depositing at least one layer of a photosensitive composition on asubstrate; (b) irradiating a portion of the layer of photosensitivecomposition with a light comprising a wavelength in a range of fromabout 250 nm to about 800 nm, or a sub-range therewithin, so as topolymerize the irradiated portion of the layer, thereby providing apatterned layer of polymerized and unpolymerized regions. Such methodsmay also further comprise removing the unpolymerized region of thepattern.

Additional embodiments provide polymerized composition or an article ofmanufacture comprising the polymerize composition as prepared accordingto any one of the methods described herein. The compositions may bepatterned layers or solid objects. In certain embodiments, thecompositions can be used to form tissue scaffolds, the scaffolds beingeither alone or populated with tissue or cell populations (for example,stem cells) and methods of treatment using such scaffolds.

While the compositions and methods are suitable for forming patternedpolymer layers, the same compositions and analogous methods can also beused to prepare three-dimensional structures. Certain embodimentsprovide, then, methods comprising; (a) depositing at least two layers ofa composition having at least one alkene or alkyne capable of undergoinga metathesis polymerization or crosslinking reaction, at least one ofwhich contains a catalyst of Formula (I), said deposition forming astacked assembly; (b) irradiating at least a portion of the stackedassembly with light, such that light penetrates and irradiates at leasttwo layers of the stacked assembly, under conditions sufficient topolymerize or crosslink at least portions of adjacent layers of thestacked assembly; wherein at least one layer contains a rutheniumcarbene 2,2′-bipyridine complex as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The present application is further understood when read in conjunctionwith the appended drawings. For the purpose of illustrating the subjectmatter, there are shown in the drawings exemplary embodiments of thesubject matter; however, the presently disclosed subject matter is notlimited to the specific methods, devices, and systems disclosed. Inaddition, the drawings are not necessarily drawn to scale. In thedrawings:

FIGS. 1A and 1B show structures of preferred catalysts of the presentdisclosure.

FIG. 2 show some of the bipyridine ligands tested in the Examples.

FIG. 3 show some of the phenanthroline ligands tested in the Examples.

FIG. 4A illustrates the dark stabilities of various latent rutheniumcatalysts containing phenanthroline and bipyridine ligands. FIG. 4Bshows the corresponding reactivites of those catalysts, as described inExample 1.

FIG. 5 is a photopolymer ‘working curve’ measuring the cure depth of thegelled material as a function of the dosage of light for a latentruthenium catalyst containing bipyridine ligand, as described in Example5.

FIG. 6 is a photopolymer ‘working curve’ measuring the cure depth of thegelled material as a function of the dosage of light for a latentruthenium catalyst containing 4,4′-di-tert-butyl-2,2′-bipyridine ligand,as described in Example 6.

FIG. 7 is a depiction of testing protocol and results described inExamples 5 and 6.

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

The present disclosure relates to method of metathesizing olefins usingcatalysts previously considered to be practically inactive. Thesemethods provide for novel photosensitive compositions, their use asphotoresists, and methods related to patterning polymer layers onsubstrates. Further, modifications to the compositions and methodprovide for an unprecedented functionalization of the compositions,useful for example in the preparation of sensors, drug delivery systems,and tissue scaffolds. The novel compositions and associated methods alsoprovide for the opportunity to prepare 3-dimensional objects whichprovide new access to critically dimensioned devices, including forexample photonic devices.

U.S. patent application Ser. No. 14/505,824, filed Oct. 3, 2014,describes the use of phenanthroline- and other aromatic diamine-basedruthenium metathesis catalysts as latent photoactivators. The presentinventor has discovered that replacing the phenanthroline ligand withany one of a range of bipyridinyl ligands results in an unexpectedlyhigher activity of the resulting metathesis catalysts, allowing forlower loadings and the ability to use less intense light sources. Thedegree of enhancement in activity is so significant that it allows theseruthenium-bipyridine catalysts to operate under conditions where thecorresponding phenantholine materials do not.

Despite the dramatic increase in photoactivity, all of the applicationsand products resulting from the use of the phenanthroline derivativesdescribed in U.S. patent application Ser. No. 14/505,824 are expected tobe applicable with these more photoactive bipyridine-substitutedmaterials. For the sake of completeness, many of the descriptions in the824 application are reiterated here.

The present disclosure may be understood more readily by reference tothe following description taken in connection with the accompanyingFigures and Examples, all of which form a part of this disclosure. It isto be understood that this disclosure is not limited to the specificproducts, methods, conditions or parameters described or shown herein,and that the terminology used herein is for the purpose of describingparticular embodiments by way of example only and is not intended to belimiting of any claimed invention. Similarly, unless specificallyotherwise stated, any description as to a possible mechanism or mode ofaction or reason for improvement is meant to be illustrative only, andthe disclosure herein is not to be constrained by the correctness orincorrectness of any such suggested mechanism or mode of action orreason for improvement. Throughout this text, it is recognized that thedescriptions refer to compositions and methods of making and using saidcompositions. That is, where the disclosure describes or claims afeature or embodiment associated with a composition or a method ofmaking or using a composition, it is appreciated that such a descriptionor claim is intended to extend these features or embodiment toembodiments in each of these contexts (i.e., compositions, methods ofmaking, and methods of using).

In the present disclosure the singular forms “a,” “an,” and “the”include the plural reference, and reference to a particular numericalvalue includes at least that particular value, unless the contextclearly indicates otherwise. Thus, for example, a reference to “amaterial” is a reference to at least one of such materials andequivalents thereof known to those skilled in the art, and so forth.

When a value is expressed as an approximation by use of the descriptor“about,” it will be understood that the particular value forms anotherembodiment. In general, use of the term “about” indicates approximationsthat can vary depending on the desired properties sought to be obtainedby the disclosed subject matter and is to be interpreted in the specificcontext in which it is used, based on its function. The person skilledin the art will be able to interpret this as a matter of routine. Insome cases, the number of significant figures used for a particularvalue may be one non-limiting method of determining the extent of theword “about.” In other cases, the gradations used in a series of valuesmay be used to determine the intended range available to the term“about” for each value. Where present, all ranges are inclusive andcombinable. That is, references to values stated in ranges include everyvalue within that range.

It is to be appreciated that certain features of the disclosure whichare, for clarity, described herein in the context of separateembodiments, may also be provided in combination in a single embodiment.That is, unless obviously incompatible or specifically excluded, eachindividual embodiment is deemed to be combinable with any otherembodiment(s) and such a combination is considered to be anotherembodiment. Conversely, various features of the disclosure that are, forbrevity, described in the context of a single embodiment, may also beprovided separately or in any sub-combination. Finally, while anembodiment may be described as part of a series of steps or part of amore general structure, each said step may also be considered anindependent embodiment in itself, combinable with others.

The transitional terms “comprising,” “consisting essentially of,” and“consisting” are intended to connote their generally in acceptedmeanings in the patent vernacular; that is, (i) “comprising,” which issynonymous with “including,” “containing,” or “characterized by,” isinclusive or open-ended and does not exclude additional, unrecitedelements or method steps; (ii) “consisting of” excludes any element,step, or ingredient not specified in the claim; and (iii) “consistingessentially of” limits the scope of a claim to the specified materialsor steps “and those that do not materially affect the basic and novelcharacteristic(s)” of the claimed invention(s). Embodiments described interms of the phrase “comprising” (or its equivalents), also provide, asembodiments, those which are independently described in terms of“consisting of” and “consisting essentially” of. For those embodimentsprovided in terms of “consisting essentially of,” the basic and novelcharacteristic(s) is the operability of the methods (or the compositionsor devices derived therefrom) as providing a photochemically activatedmetathesis system using the bipyridine-ligated catalysts, for example,as shown in FIG. 1.

When a list is presented, unless stated otherwise, it is to beunderstood that each individual element of that list, and everycombination of that list, is a separate embodiment. For example, a listof embodiments presented as “A, B, or C” is to be interpreted asincluding the embodiments, “A,” “B,” “C,” “A or B,” “A or C,” “B or C,”or “A, B, or C.”

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The present invention(s) include a range of pre-polymerized compositionscomprising at least one ruthenium carbene metathesis catalyst, methodsof polymerizing these compositions, as well as their polymerizedproducts, including the specific devices or articles derived therefrom.While not intending to be limited to any particular embodiment(s), thesenovel and non-obvious compositions may be described as including (1)ruthenium carbene metathesis catalysts containing bipyridine ligands,operable over the range of polymer compositions, structures andproducts; (2) olefin precursors and polymerizable matrices, each ofwhich may include any one or more of the range of ruthenium carbenemetathesis catalysts described herein; and (3) superstructures which canbe prepared using any one or more of ruthenium carbene metathesiscatalyst and one or more reactive polymers or polymerizable matrices.Each of these is described more fully below. For wording efficiency, thevarious elements of the disclosure(s) are described individually, thoughit should be recognized that the disclosure contemplates combinationsthereof.

General Metathesis Description

The present disclosure describes compositions which are novel both intheir choice of olefinic substrates and in the catalysts used to preparethe prepolymerized and polymerized compositions. These novelcombinations of substrates and catalysts offer materials which exhibitproperties or ways of handling these materials not previouslyrecognized. In particular, these bipyridine-containing rutheniumcatalysts exhibit a reactivity vastly and unexpectedly superior to theirphenanthroline cousins. These substrates and catalysts will be discussedseparately, but it should be appreciated that the present disclosureconsiders each combination to be within the scope of the presentinvention(s).

The present disclosure includes embodiments related to compositions andmethods of metathesizing unsaturated organic precursors, each methodcomprising irradiating a Fischer-type carbene ruthenium metathesiscatalyst of Formula (I) with at least one wavelength of light in thepresence of at least one unsaturated organic precursor, so as tometathesize at least one alkene or one alkyne bond within the matricesof the at least one precursors. For purposes of the present disclosure,so-called “Fischer-type” carbenes are defined, as comprising anon-persistent carbene having pi-donor substituents, such as alkoxy andalkylated amino groups, as well as hydrogen and alkyl substituents onthe non-persistent carbenoid carbon. Alkoxy and alkylated amino groupson the carbene carbon render Fischer-type carbenes, especially those ofruthenium, virtually inert relative to their “Schrock-type” cogeners. Infact, the addition of substituted vinyl ethers or vinyl amines, forexample, can virtually inactivate a ruthenium metathesis catalystcontaining a “Schrock-type” carbene, by forming the correspondingFischer-type derivative. These Fischer-type carbene complexes are widelyconsidered inactive due to the electronics of the carbene. In fact,ethyl vinyl ether is commonly used to quench ROMP (Ring OpeningMetathesis Polymerization) reactions. The following descriptions nowdemonstrate that these Ruthenium complexes and their “quenched”derivatives undergo further chemistry when photochemically activated.

Catalysts

In certain embodiments, the Fischer-type carbene ruthenium metathesiscatalyst used in the photochemically activated metathesis compositionsis a metathesis catalyst of Formula (I):

where:

X¹ and X² are independently anionic ligands;

Y is O, N—R¹, or S, preferably O; and

Q is a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or—CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, andR¹⁴ are independently hydrogen an optionally substituted hydrocarbyl;

R¹ and R² are independently hydrogen or optionally substitutedhydrocarbyl, or R¹ and R² may be linked together to form an optionallysubstituted cyclic aliphatic group;

R³ and R⁴ are independently optionally substituted hydrocarbyl; and

R⁵ and R⁶ are independently H or electron-withdrawing orelectron-donating groups, including C₁₋₂₄alkyl, C₁₋₂₄alkoxy,C₁₋₂₄fluoroalkyl, C₁₋₂₄fluoroalkoxy, C₁₋₂₄alkylhydroxy,C₁₋₂₄alkoxyhydroxy, C₁₋₂₄fluoroalkylhydroxy(includingperfluoroalkylhydroxy), C₁₋₂₄fluoroalkoxyhydroxy, halo, cyano, nitro, orhydroxy; and

m and n are independently 1, 2, 3, or 4.

The ruthenium carbene metathesis catalyst of Formula (I) may be added asdescribed here or generated in situ as described herein. The independentX¹ and X² are anionic ligands are believed to be positioned cis withrespect to one another, though the compounds may also be present asgeometric isomers of the structure as presented.

X¹ and X² are anionic ligands, and may be the same or different, or arelinked together to form a cyclic group, typically although notnecessarily a five- to eight-membered ring. In preferred embodiments, X¹and X² are each independently hydrogen, halide, or one of the followinggroups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy,C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, NO₃, —N═C═O, —N═C═S, orC₅-C₂₄ arylsulfinyl. Optionally, X¹ and X² may be substituted with oneor more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl,and halide, which may, in turn, with the exception of halide, be furthersubstituted with one or more groups selected from halide, C₁-C₆ alkyl,C₁-C₆ alkoxy, and phenyl. In more preferred embodiments, X¹ and X² arehalide, benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl,phenoxy, C₁-C₆ alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆alkylsulfonyl. In even more preferred embodiments, X¹ and X² are eachhalide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO,PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In themost preferred embodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g.,C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), andsubstituted heteroatom-containing hydrocarbyl (e.g., substitutedheteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functionalgroups. R¹ and R² may also be linked to form a cyclic group. Generally,such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ringatoms. In certain embodiments, R² is not hydrogen.

In some embodiments, R¹ is hydrogen and R² is selected from C₁-C₂₀alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, more preferably C₁-C₆ alkyl,C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still more preferably, R² is phenyl,methyl, ethyl, isopropyl, or t-butyl, optionally substituted with one ormore moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, and afunctional group Fn as defined earlier herein. Most preferably, R² isphenyl or ethyl optionally substituted with one or more moietiesselected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro,dimethylamino, methyl, methoxy, and phenyl. Optimally, R² is phenyl,ethyl, propyl, or butyl.

In certain of these embodiments, Ru═C(R¹)(Y—R²) moiety is a substitutedvinyl ether carbene. In independent embodiments, R² is C₁₋₆ alkyl,preferably ethyl, propyl, or butyl. In other embodiments, R¹ is H, R² isC₁₋₆ alkyl, and Y is O.

In certain of embodiments, the moiety:

is an N-heterocyclic carbene (NHC) ligand. In some embodiments, R³ andR⁴ are as defined above, with preferably at least one of R³ and R⁴, andmore preferably both R³ and R⁴, being alicyclic or aromatic of one toabout five rings, and optionally containing one or more heteroatomsand/or substituents. Q is a linker, typically a hydrocarbylene linker,including substituted hydrocarbylene, heteroatom-containinghydrocarbylene, and substituted heteroatom-containing hydrocarbylenelinkers, wherein two or more substituents on adjacent atoms within Q mayalso be linked to form an additional cyclic structure, which may besimilarly substituted to provide a fused polycyclic structure of two toabout five cyclic groups. Q is often, although not necessarily, atwo-atom linkage or a three-atom linkage.

Examples of N-heterocyclic carbene (NHC) ligands and acyclicdiaminocarbene ligands include, but are not limited to, the followingwhere DIPP or DiPP is diisopropylphenyl and Mes is2,4,6-trimethylphenyl:

Additional examples of N-heterocyclic carbene (NHC) ligands and acyclicdiaminocarbene ligands suitable as L¹ thus include, but are not limitedto the following:

wherein R^(W1), R^(W2), R^(W3), R^(W4) are independently hydrogen,unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatomcontaining hydrocarbyl, and where one or both of R^(W3) and R^(W4) maybe in independently selected from halogen, nitro, amido, carboxyl,alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

Additional examples of suitable N-heterocyclic carbene (NHC) ligands arefurther described in U.S. Pat. Nos. 7,378,528; 7,652,145; 7,294,717;6,787,620; 6,635,768; and 6,552,139 the contents of each areincorporated herein by reference.

In a more preferred embodiment, Q is a two-atom linkage having thestructure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably—CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independentlyselected from hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Examples of functional groups hereinclude without limitation carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy,C₂-C₂₀ alkoxycarbonyl, C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀alkylthio, C₅-C₂₄ arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀alkylsulfinyl, optionally substituted with one or more moieties selectedfrom C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl,formyl, and halide. R¹¹, R¹², R¹³, and R¹⁴ are preferably independentlyselected from hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂heteroalkyl, substituted C₁-C₁₂ heteroalkyl, phenyl, and substitutedphenyl. Alternatively, any two of R¹¹, R¹², R¹³, and R¹⁴ may be linkedtogether to form a substituted or unsubstituted, saturated orunsaturated ring structure, e.g., a C₄-C₁₂ alicyclic group or a C₅ or C₆aryl group, which may itself be substituted, e.g., with linked or fusedalicyclic or aromatic groups, or with other substituents. In one furtheraspect, any one or more of R¹¹, R¹², R¹³, and R¹⁴ comprises one or moreof the linkers. Additionally, R³ and R⁴ may be unsubstituted phenyl orphenyl substituted with one or more substituents selected from C₁-C₂₀alkyl, substituted C₁-C₂₀ alkyl, C₁—C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl,C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Furthermore, X¹ and X² may behalogen.

When R³ and R⁴ are aromatic, they are typically although not necessarilycomposed of one or two aromatic rings, which may or may not besubstituted, e.g., R³ and R⁴ may be phenyl, substituted phenyl,biphenyl, substituted biphenyl, or the like. In one preferredembodiment, R³ and R⁴ are the same and are each unsubstituted phenyl orphenyl substituted with up to three substituents selected from C₁-C₂₀alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl,C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Preferably, any substituentspresent are hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl,substituted C₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ are mesityl(i.e. Mes as defined herein).

In some preferred embodiments, Q may be defined as having the structure—CH₂—CH₂— and either R³ or R⁴, or both R³ and R⁴ are phenyl groups,optionally substituted in the 2, 4, 6 positions with independent C₁₋₆alkyl groups, where C₃₋₆ alkyl groups may be branched or linear, e.g.,including methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl,tert-butyl. In certain preferred embodiments, the phenyl groups areoptionally substituted in the 2, 6 positions with independent C₁₋₆ alkylgroups, and the 4-position is optionally substituted with anelectron-withdrawing or—donating group as described herein, for example,alkyl, alkoxy, nitro, or halo. In other embodiments, Q is —CH₂—CH₂— andR³ and R⁴ are independently mesityl or optionally substituted adamantyl.

The bipyridine substituents, R⁵ and R⁶ are described as independently Hor electron-withdrawing or electron-donating groups, includingC₁₋₂₄alkyl, C₁₋₂₄alkoxy, C₁₋₂₄fluoroalkyl, C₁₋₂₄fluoroalkoxy,C₁₋₂₄alkylhydroxy, C₁₋₂₄alkoxyhydroxy, C₁₋₂₄fluoroalkylhydroxy(includingperfluoroalkylhydroxy), C₁₋₂₄fluoroalkoxyhydroxy, halo, cyano, nitro, orhydroxy; and m and n are described as independently 1, 2, 3, or 4. Theelectron-withdrawing groups (EWG) or electron-donating groups (EDG) maymore broadly include, independently at each occurrence, —NH₂, —NHR, —NR₂(where R is C₁₋₁₈ alkyl), hydroxide, C₁₋₁₈ alkoxide, —NHC(O)(C₁₋₁₈alkyl), C₁₋₁₈ alkyl, C₆₋₁₀ aryl, nitro, quaternary amines, halo- orperhalo-C₁₋₁₈ alkyl, —CN, —C₀₋₆ alkylsulfonate, —C₀₋₆ alkyl phosphonate,—C₁₋₆ alkyl-C(O)—R (where R is C₁₋₁₈ alkyl), or —C₁₋₆alkoxycarbonyls. Inpreferred embodiments, the EWG or EDG include, independently at eachoccurrence —NH₂, —NHR, —NR₂ (where R is C₁₋₃ alkyl), hydroxide, C₁₋₃alkoxide, —NHC(O)(C₁₋₃ alkyl), C₁₋₆ alkyl, C₆aryl, nitro, quaternaryamines, CF₃, —CN, —C₁₋₆ alkylsulfonate, —C₀₋₃ alkyl phosphonate,-carboxylate, or —C₁₋₃alkoxycarbonyl, silyl, or phosphonyl.

In preferred embodiments, R⁵ and R⁶ are independently H, methyl, ethyl,propyl, butyl, methoxy, trifluoromethyl, fluoro, chloro, bromo, cyano,or nitro.

Each R⁵ and R⁶ may be independently positioned one their ring, thoughtypically they are positioned on the corresponding positions. That is,one or more of R⁵ may be present in any one or more of the 3, 4, 5, or 6positions, and R⁶ may be independently present in any one or more of the3′, 4′, 5′, or 6′ positions. But in preferred embodiments, theoptionally substituted 2,2′-bipyridine is substituted with R⁵ and R⁶ inthe 3,3′ or 4,4′ or 5,5′ or 6,6′ positions, most preferably in the 4,4′or 5,5′ positions:

A ruthenium catalyst having a structure of Formula (IA) has been foundto be especially useful in the disclosed compositions and methods:

These ruthenium-bipyridine catalysts may be provided to the compositionsas shown, or may be generated in situ by the mixing of an optionallysubstituted 2,2′-bipyridine, a quenching agent of

and a metathesis catalyst of Formula (IIA), (IIB), (IIIA), or (IIIB); ora geometric isomer thereof:

wherein:

L³ and L⁴ are independently neutral electron donor ligands;

k and n are independently 0 or 1; and

R^(A), and R^(B) are independently hydrogen or optionally substitutedhydrocarbyl, or may be linked to form an optionally substituted aromaticor aliphatic cyclic group,

where Q, X¹, X², R³, and R⁴ are as described elsewhere herein.

Such structures include:

Throughout this specification, words are to be afforded their normalmeaning, as would be understood by those skilled in the relevant art.However, so as to avoid misunderstanding, the meanings of certain termswill be specifically defined or clarified.

The term “anionic ligands” refer to those ligands coordinated to a metalcental, which are more electronegative than the metal to an extent thatthey are typically considered to carry a negative charge. Alternatively,if not coordinated to a metal center as a ligand, they would be anions.Such ligands, for example, include chloride, bromide, nitrate, sulfate,etc.

Where a given catalyst structure is provided, that structure isconsidered a specific embodiment. However, it should be appreciated thatcatalytic cycles by their nature involve transient intermediates orcompounds which are transformed during the course of their reaction. Assuch, the term catalyst, when applied to a given structure, should alsobe considered to include those transient structures associated with thecatalytic cycles of the provided structures. Additionally, the actualstructure may be a geometric isomer of that actually shown. Geometricisomers are two or more coordination compounds which contain the samenumber and types of atoms, and bonds (i.e., the connectivity betweenatoms is the same), but which have different spatial arrangements of theatoms around the metal center. The isomer in which like ligands areadjacent to one another is called the cis isomer.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,”“substituted aryl,” and the like, as alluded to in some of theaforementioned definitions, is meant that in the hydrocarbyl, alkyl,aryl, heteroaryl, or other moiety, at least one hydrogen atom bound to acarbon (or other) atom is replaced with one or more non-hydrogensubstituents. Examples of such substituents include, without limitation:functional groups referred to herein as “Fn,” such as halo (e.g., F, Cl,Br, I), hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl(including C₁-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl(—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO—alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl((CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl(—CO)—X where X is halo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl),C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxy (—COOH), carboxylato(—COO—), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substitutedcarbamoyl (—(CO)NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substitutedcarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₁-C₂₄ haloalkyl)-substitutedcarbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ haloalkyl)-substitutedcarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substitutedcarbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl) substituted carbamoyl(—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄alkyl)-substituted thiocarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄aryl) substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄aryl)-substituted thiocarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl, carbamido(—NH—(CO)—NH₂), cyano(-C≡N), cyanato (—O—C═N), thiocyanato (—S—C═N),formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄alkyl)-substituted amino, di-(C₁-C₂₄ alkyl)-substituted amino,mono-(C₅-C₂₄ aryl) substituted amino, di-(C₅-C₂₄ aryl)-substitutedamino, C₁-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄ arylamido(—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), C₂-C₂₀ alkylimino(—CR═N(alkyl), where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), whereR=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl,etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂OH), sulfonate(SO₂O—),C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C₅-C₂₄arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄ alkylsulfinyl(—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄ alkylsulfonyl(—SO₂-alkyl), C₁-C₂₄ monoalkylaminosulfonyl-SO₂—N(H) alkyl), C₁-C₂₄dialkylaminosulfonyl-SO₂—N(alkyl)₂, C₅-C₂₄ arylsulfonyl (—SO₂-aryl),boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl orother hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O)₂),phosphinato (P(O)(O—)), phospho (—PO₂), and phosphine (—PH₂); and thehydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, morepreferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, morepreferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl,more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferably C₅-C₂₄ aryl),C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl(preferably C₆-C₁₆ aralkyl). Within these substituent structures, the“alkyl,” “alkylene,” “alkenyl,” “alkenylene,” “alkynyl,” “alkynylene,”“alkoxy,” “aromatic,” “aryl,” “aryloxy,” “alkaryl,” and “aralkyl”moieties may be optionally fluorinated or perfluorinated. Additionally,reference to alcohols, aldehydes, amines, carboxylic acids, ketones, orother similarly reactive functional groups also includes their protectedanalogs. For example, reference to hydroxy or alcohol also includesthose substituents wherein the hydroxy is protected by acetyl (Ac),benzoyl (Bz), benzyl (Bn, Bnl), β-Methoxyethoxymethyl ether (MEM),dimethoxytrityl, [bis-(4-methoxyphenyl)phenylmethyl] (DMT),methoxymethyl ether (MOM), methoxytrityl[(4-methoxyphenyl)diphenylmethyl, MMT), p-methoxybenzyl ether (PMB),methylthiomethyl ether, pivaloyl (Piv), tetrahydropyranyl (THP),tetrahydrofuran (THF), trityl (triphenylmethyl, Tr), silyl ether (mostpopular ones include trimethylsilyl (TMS), tert-butyldimethylsilyl(TBDMS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl(TIPS) ethers), ethoxyethyl ethers (EE). Reference to amines alsoincludes those substituents wherein the amine is protected by a BOCglycine, carbobenzyloxy (Cbz), p-methoxybenzyl carbonyl (Moz or MeOZ),tert-butyloxycarbonyl (BOC), 9-fluorenylmethyloxycarbonyl (FMOC), acetyl(Ac), benzoyl (Bz), benzyl (Bn), carbamate, p-methoxybenzyl (PMB),3,4-dimethoxybenzyl (DMPM), p-methoxyphenyl (PMP), tosyl (Ts) group, orsulfonamide (Nosyl & Nps) group. Reference to substituent containing acarbonyl group also includes those substituents wherein the carbonyl isprotected by an acetal or ketal, acylal, or diathane group. Reference tosubstituent containing a carboxylic acid or carboxylate group alsoincludes those substituents wherein the carboxylic acid or carboxylategroup is protected by its methyl ester, benzyl ester, tert-butyl ester,an ester of 2,6-disubstituted phenol (e.g. 2,6-dimethylphenol,2,6-diisopropylphenol, 2,6-di-tert-butylphenol), a silyl ester, anorthoester, or an oxazoline.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalizedalkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and thelike, is meant that in the hydrocarbyl, alkyl, aryl, heteroaryl, olefin,cyclic olefin, or other moiety, at least one hydrogen atom bound to acarbon (or other) atom is replaced with one or more functional groupssuch as those described herein and above. The term “functional group” ismeant to include any functional species that is suitable for the usesdescribed herein. In particular, as used herein, a functional groupwould necessarily possess the ability to react with or bond tocorresponding functional groups on a substrate surface.

“Optional” or “optionally” means that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

In some embodiments, L⁴ is phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, (including cyclicethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine,substituted pyridine, imidazole, substituted imidazole, pyrazine,substituted pyrazine or thioether. Exemplary ligands are trisubstitutedphosphines. Preferred trisubstituted phosphines are of the formulaPR^(H1)R^(H2)R^(H3), where R^(H1), R^(H2), and R^(H3) are eachindependently substituted or unsubstituted aryl or C₁-C₁₀ alkyl,particularly primary alkyl, secondary alkyl, or cycloalkyl. In otherembodiments L⁴ is trimethylphosphine (PMe₃), triethylphosphine (PEt₃),tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃),tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine(PCyclopentyl₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine(P-i-Pr₃), trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃),triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃),methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), ordiethylphenylphosphine (PEt₂Ph).

In other embodiments, L³ and L⁴ include, without limitation,heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L³ and L⁴include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine,pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole,2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole,1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine,indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline,cinnoline, quinazoline, naphthyridine, piperidine, piperazine,pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine,purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.Additionally, the nitrogen-containing heterocycles may be optionallysubstituted on a non-coordinating heteroatom with a non-hydrogensubstitutent.

Examples of sulfur-containing heterocycles appropriate for L³ and L⁴include thiophene, 1,2-dithiole, 1,3-dithiole, thiepin,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L³ and L⁴include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin,oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene,chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene,tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

Examples of mixed heterocycles appropriate for L³ and L⁴ includeisoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole,1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole,1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine,1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine,pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, andmorpholine.

Preferred L³ and L⁴ ligands are aromatic nitrogen-containing andoxygen-containing heterocycles, and particularly preferred L³ and L⁴ligands are monocyclic N-heteroaryl ligands that are optionallysubstituted with 1 to 3, preferably 1 or 2, substituents. Specificexamples of particularly preferred L³ and L⁴ ligands are pyridine andsubstituted pyridines, such as 3-bromopyridine, 4-bromopyridine,3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine,3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine,2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine,3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,3,5-dichloro-4-phenylpyridine, and the like.

Photochemical Conditions

As used herein, and unless otherwise stated, the term “activates” refersto the fact that the irradiated catalyst metathesizes (i.e., polymerizesor crosslinks) olefins or alkynes at a rate that is faster at least 10times faster than metathesizes the same olefins or alkynes beforeirradiation. Having said this, and when so specified, independentembodiments provide that the irradiated catalyst metathesizes olefins oralkynes at a rate that is faster at least 2 times, 5 times, 50 times,100 times, or 1000 times faster than the metathesis of the same olefinsor alkynes before or without irradiation.

The present ruthenium-bipyridine catalysts allow for the use of simpleLED sources, which illuminate at a single wavelength and at lowerenergies, in contrast to Hg lamps typically used in mask aligners. Thesebipyridine coordination complexes show reactivity at one or morewavelengths in a range of from about 250 to about 800 nm, from about 300to about 500 nm, or in a range of from about 340 to about 460 nm,preferably in a range of from about 380 to about 420 nm. Additionalembodiments provide that the light comprises at least one wavelength ina range of from about 250 to about 300 nm, from about 300 to about 320nm, from about 320 to about 340 nm, from about 340 to about 360 nm, fromabout 360 to about 380 nm, from about 380 to about 400 nm, from about400 to about 420 nm, from about 420 to about 440 nm, from about 440 toabout 460 nm, from about 460 to about 480 nm, from about 480 to about500 nm, from about 500 to about 600 nm, from about 600 to about 700 nm,from about 700 to about 800 nm, or a combination thereof. This isconsistent with currently available dry-polymer photopolymers used inthe printed circuit industry (e.g. photoresist and solder mask) functionwhen exposed to ultraviolet (UV) radiation in the range of about 300 nmto about 440 nm in a production environment.

Additional embodiments provide that the compositions may be activated bytwo- or three-photon energy sources, for example, using a focused 790 nmlaser to provide three-dimensional structures written using thismulti-photon absorption. Other multi-photon lithography methods may alsobe employed, including interference lithography techniques such as phasemask lithography and proximity field nanopatterning. Other patterningstrategies, including nanoimprint lithography, substrate conformalimprint lithography, stimulated emission and depletion lithography, arealso methods which can be used in concert with the present compositionsand methods.

In particular, nanoimprint lithography is a technique that is widelyused to replicate nanostructured layers. This technique has theadvantage that the imprinting stamp can be reused many times. Thetime-intensive process of making a ‘master’ for the stamp need only beperformed once, enabling rapid duplication applicable to industrialscale micro- and nanofabrication. This method has been shown to beapplicable with the present methods and compositions, thereby enablingthe rapid and large-area fabrication of chemically functionalnanostructures.

Similarly, these Fischer-type carbene ruthenium metathesis catalystsbecome activated after being irradiated with a light having an intensityin a range of 1 mW/cm² to 10 W/cm², preferably about 10 mW/cm² to 200mW/cm², at one or more wavelength in one of the ranges described above,for example in a range of about 220 to 440 nm. For some systems,depending on the reactivity of the specific catalyst and/or olefins, theenergy of sunlight is sufficient to activate these materials. It isexpected that the catalysts described herein will work at these levels,if necessary to go there.

Unsaturated Precursors

The methods of the present disclosure also consider that theFischer-type carbene ruthenium metathesis catalyst as described herein,may be dissolved in a solvent in the presence of at least oneunsaturated organic precursor or are admixed or dissolved in at leastone unsaturated organic precursor. As used herein, the term “at leastone unsaturated organic precursor” is intended to connote one or moremolecular compound or oligomer, or combination thereof, each comprisingat least one olefinic (alkene) or one acetylenic (alkyne) bond permolecule or oligomeric unit. These precursors comprise cyclic oralicyclic cis- or trans-olefins or cyclic or alicyclic acetylenes, or astructure having both types of bonds (including alicyclic or cyclicenynes).

The photosensitive, polymerizable compositions may also be described asbeing dissolved or admixed within polymerizable material matrix. Suchmatrices include those comprising polymers, polymer precursors, or acombination thereof, provided that the matrix contains at least oneolefinic (alkene) or one acetylenic (alkyne) bond per molecule,oligomeric unit, or polymeric unit. Such compositions may includecrosslinking polymers. In some cases, the mixture of polymerized andnon-polymerized materials may result from the incomplete polymerizationof the polymer precursor. In other cases, the polymerized andnon-polymerized materials may be chemically unrelated.

The inventive compositions and methods may also comprise alkynylprecursors. As used herein, the term “alkynyl” (or “acetylenic”) or“alkyne” refers to a linear or branched hydrocarbon group or compound of2 to about 24 carbon atoms containing at least one triple bond, such asethynyl, n-propynyl, and the like. Preferred alkynyl groups hereincontain 2 to about 12 carbon atoms, preferably containing a terminalalkyne bond. The term “lower alkynyl” refers to an alkynyl group of 2 to6 carbon atoms. The term “substituted alkynyl” refers to alkynylsubstituted with one or more substituent groups. As used herein, theterms “optional” or “optionally” mean that the subsequently describedcircumstance may or may not occur, so that the description includesinstances where the circumstance occurs and instances where it does not.For example, the phrase “optionally substituted” means that anon-hydrogen substituent may or may not be present on a given atom, and,thus, the description includes structures wherein a non-hydrogensubstituent is present and structures wherein a non-hydrogen substituentis not present.

Olefinic precursors may be used in tandem with the alkynes, eitheremployed as part of the feedstock mixtures, or in sequential processingof the product polymers. Suitable options for such precursors are thosering systems, particularly strained ring systems, which are useful forROMP reactions. One such class of compounds in this regard issubstituted or unsubstituted cyclooctatetraenes, includingcyclooctatetraene itself.

As described above, suitable options for such olefinic or acetylenicprecursors include ring systems, particularly strained ring systems,which are useful for ROMP reactions. Such cyclic olefins may beoptionally substituted, optionally heteroatom-containing,mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefinmay generally be any strained or unstrained cyclic olefin, provided thecyclic olefin is able to participate in a ROMP reaction eitherindividually or as part of a ROMP cyclic olefin composition. Whilecertain unstrained cyclic olefins such as cyclohexene are generallyunderstood to not undergo ROMP reactions by themselves, underappropriate circumstances, such unstrained cyclic olefins maynonetheless be ROMP active. For example, when present as a co-monomer ina ROMP composition, unstrained cyclic olefins may be ROMP active.Accordingly, as used herein and as would be appreciated by the skilledartisan, the term “unstrained cyclic olefin” is intended to refer tothose unstrained cyclic olefins that may undergo a ROMP reaction underany conditions, or in any ROMP composition, provided the unstrainedcyclic olefin is ROMP active.

In general, the cyclic olefin may be represented by the structure offormula (A)

wherein J, R^(A1), and R^(A2) are as follows:

R^(A1) and R^(A2) is selected independently from the group consisting ofhydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl,or C₅-C₃₀ alkaryl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl),heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₀heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl), and substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as alkene, alkyne, phosphonato,phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀ arylsulfonyl, C₁-C₂₀alkylsulfinyl, C₅-C₂₀ arylsulfinyl, sulfonamido, amino, amido, imino,nitro, nitroso, hydroxyl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, carboxyl, carboxylato, mercapto,formyl, C₁-C₂₀ thioester, cyano, cyanato, thiocyanato, isocyanate,thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl,siloxazanyl, boronato, boryl, or halogen, or a metal-containing ormetalloid-containing group (wherein the metal may be, for example, Sn orGe). R^(A1) and R^(A) may itself be one of the aforementioned groups,such that the Fn moiety is directly bound to the olefinic carbon atomindicated in the structure. In the latter case, however, the functionalgroup will generally not be directly bound to the olefinic carbonthrough a heteroatom containing one or more lone pairs of electrons,e.g., an oxygen, sulfur, nitrogen, or phosphorus atom, or through anelectron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc.With such functional groups, there will normally be an interveninglinkage Z*, such that R^(A1) and/or R^(A2) then has the structure—(Z*)_(n)-Fn wherein n is 1, Fn is the functional group, and Z* is ahydrocarbylene linking group such as an alkylene, substituted alkylene,heteroalkylene, substituted heteroalkene, arylene, substituted arylene,heteroarylene, or substituted heteroarylene linkage.

J is a saturated or unsaturated hydrocarbylene, substitutedhydrocarbylene, heteroatom-containing hydrocarbylene, or substitutedheteroatom-containing hydrocarbylene linkage, wherein when J issubstituted hydrocarbylene or substituted heteroatom-containinghydrocarbylene, the substituents may include one or more —(Z*)_(n)-Fngroups, wherein n is zero or 1, and Fn and Z* are as defined previously.Additionally, two or more substituents attached to ring carbon (orother) atoms within J may be linked to form a bicyclic or polycyclicolefin. J will generally contain in the range of approximately 5 to 14ring atoms, typically 5 to 8 ring atoms, for a monocyclic olefin, and,for bicyclic and polycyclic olefins, each ring will generally contain 4to 8, typically 5 to 7, ring atoms.

Mono-unsaturated cyclic olefins encompassed by structure (A) may berepresented by the structure (B)

wherein b is an integer generally although not necessarily in the rangeof 1 to 10, typically 1 to 5,

R^(A1) and R^(A2) are as defined above for structure (A), and R^(B1),R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) are independently selectedfrom the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl and —(Z*)_(n)-Fn where n, Z* and Fnare as defined previously, and wherein if any of the R^(B1) throughR^(B6) moieties is substituted hydrocarbyl or substitutedheteroatom-containing hydrocarbyl, the substituents may include one ormore —(Z*)_(n)-Fn groups. Accordingly, R^(B1), R^(B2), R^(B3), R^(B4),R^(B5), and R^(B6) may be, for example, hydrogen, hydroxyl, C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, amino, amido, nitro, etc.

Furthermore, any of the R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), andR^(B6) moieties can be linked to any of the other R^(B1), R^(B2),R^(B3), R^(B4), R^(B5), and R^(B6) moieties to provide a substituted orunsubstituted alicyclic group containing 4 to 30 ring carbon atoms or asubstituted or unsubstituted aryl group containing 6 to 18 ring carbonatoms or combinations thereof and the linkage may include heteroatoms orfunctional groups, e.g. the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The alicyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain monounsaturation ormultiunsaturation, with monounsaturated cyclic groups being preferred.When substituted, the rings contain monosubstitution ormultisubstitution wherein the substituents are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as definedpreviously, and functional groups (Fn) provided above.

Examples of mono-unsaturated, monocyclic olefins encompassed bystructure (B) include, without limitation, cyclopentene, cyclohexene,cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene,cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, andcycloeicosene, and substituted versions thereof such as1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene,l-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene,4-methoxy-cyclopentene, 4-ethoxy-cyclopentene, cyclopent-3-ene-thiol,cyclopent-3-ene, 4-methylsulfanyl-cyclopentene, 3-methylcyclohexene,1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

Monocyclic diene reactants encompassed by structure (A) may be generallyrepresented by the structure (C)

wherein c and d are independently integers in the range of 1 to about 8,typically 2 to 4, preferably 2 (such that the reactant is acyclooctadiene), R^(A1) and R^(A2) are as defined above for structure(A), and R^(C1), R^(C2), R^(C3), R^(C4), R^(C5), and R^(C6) are definedas for R^(B1) through R^(B6). In this case, it is preferred that R^(c3)and R^(C4) be non-hydrogen substituents, in which case the secondolefinic moiety is tetrasubstituted. Examples of monocyclic dienereactants include, without limitation, 1,3-cyclopentadiene,1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene,1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene,1,3-cyclooctadiene, and substituted analogs thereof. Triene reactantsare analogous to the diene structure (C), and will generally contain atleast one methylene linkage between any two olefinic segments.Bicyclic and polycyclic olefins encompassed by structure (A) may begenerally represented by the structure (D)

wherein R^(A1) and R^(A2) are as defined above for structure (A),R^(D1), R^(D2), R^(D3), and R^(D4) are as defined for R^(B1) throughR^(B6), e is an integer in the range of 1 to 8 (typically 2 to 4) f isgenerally 1 or 2; T is lower alkylene or alkenylene (generallysubstituted or unsubstituted methyl or ethyl), CHR^(G1), C(R^(G1))₂, O,S, N—R^(G1), P—R^(G1), O═P—R^(G1), Si(R^(G1))₂, B—R^(G1), or As—R^(G1)where R^(G1) is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl,aralkyl, or alkoxy. Furthermore, any of the R^(D1), R^(D2), R^(D3), andR^(D4) moieties can be linked to any of the other R^(D1), R^(D2),R^(D3), and R^(D4) moieties to provide a substituted or unsubstitutedalicyclic group containing 4 to 30 ring carbon atoms or a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms orcombinations thereof and the linkage may include heteroatoms orfunctional groups, e.g. the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.The cyclic group can be monocyclic, bicyclic, or polycyclic. Whenunsaturated the cyclic group can contain mono-unsaturation ormulti-unsaturation, with mono-unsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution ormulti-substitution wherein the substituents are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z* and Fn are as definedpreviously, and functional groups (Fn) provided above.

Cyclic olefins encompassed by structure (D) are in the norbornenefamily. As used herein, norbornene means any compound that includes atleast one norbornene or substituted norbornene moiety, including withoutlimitation norbornene, substituted norbornene(s), norbomadiene,substituted norbornadiene(s), polycyclic norbornenes, and substitutedpolycyclic norbornene(s). Norbornenes within this group may be generallyrepresented by the structure (E)

wherein R^(A1) and R^(A2) are as defined above for structure (A), T isas defined above for structure (D), R^(E1), R^(E2), R^(E3), R^(E4),R^(E5), R^(E6), R^(E7), and R^(E8) are as defined for R^(B1) throughR^(B6), and “a” represents a single bond or a double bond, f isgenerally 1 or 2, “g” is an integer from 0 to 5, and when “a” is adouble bond one of R^(E5), R^(E6) and one of R^(E7), R^(E8) is notpresent.Furthermore, any of the R^(E5), R^(E6), R^(E7), and R^(E8) moieties canbe linked to any of the other R^(E5), R^(E6), R^(E7), and R^(E8)moieties to provide a substituted or unsubstituted alicyclic groupcontaining 4 to 30 ring carbon atoms or a substituted or unsubstitutedaryl group containing 6 to 18 ring carbon atoms or combinations thereofand the linkage may include heteroatoms or functional groups, e.g. thelinkage may include without limitation an ether, ester, thioether,amino, alkylamino, imino, or anhydride moiety. The cyclic group can bemonocyclic, bicyclic, or polycyclic. When unsaturated the cyclic groupcan contain monounsaturation or multiunsaturation, with monounsaturatedcyclic groups being preferred. When substituted, the rings containmonosubstitution or multisubstitution wherein the substituents areindependently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

More preferred cyclic olefins possessing at least one norbornene moietyhave the structure (F):

wherein, R^(F1), R^(F2), R^(F3), and R^(F4), are as defined for R^(B1)through R^(B6), and “a” represents a single bond or a double bond, “g”is an integer from 0 to 5, and when “a” is a double bond one of R^(F),R^(F2) and one of R^(F3), R^(F4) is not present.

Furthermore, any of the R^(E1), R^(F2), R^(F3), and R^(F4) moieties canbe linked to any of the other R^(F1), R^(F2), R^(F3), and R^(F4)moieties to provide a substituted or unsubstituted alicyclic groupcontaining 4 to 30 ring carbon atoms or a substituted or unsubstitutedaryl group containing 6 to 18 ring carbon atoms or combinations thereofand the linkage may include heteroatoms or functional groups, e.g. thelinkage may include without limitation an ether, ester, thioether,amino, alkylamino, imino, or anhydride moiety. The alicyclic group canbe monocyclic, bicyclic, or polycyclic. When unsaturated the cyclicgroup can contain monounsaturation or multiunsaturation, withmonounsaturated cyclic groups being preferred. When substituted, therings contain monosubstitution or multisubstitution wherein thesubstituents are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, —(Z*)_(n)-Fn where n is zero or 1, Z*and Fn are as defined previously, and functional groups (Fn) providedabove.

One route for the preparation of hydrocarbyl substituted andfunctionally substituted norbornenes employs the Diels-Aldercycloaddition reaction in which cyclopentadiene or substitutedcyclopentadiene is reacted with a suitable dienophile at elevatedtemperatures to form the substituted norbornene adduct generally shownby the following reaction Scheme 1:

wherein R^(F1) to R^(F4) are as previously defined for structure (F).

Other norbornene adducts can be prepared by the thermal pyrolysis ofdicyclopentadiene in the presence of a suitable dienophile. The reactionproceeds by the initial pyrolysis of dicyclopentadiene tocyclopentadiene followed by the Diels-Alder cycloaddition ofcyclopentadiene and the dienophile to give the adduct shown below inScheme 2:

wherein “g” is an integer from 0 to 5, and R^(F1) to R^(F4) are aspreviously defined for structure (F).

Norbornadiene and higher Diels-Alder adducts thereof similarly can beprepared by the thermal reaction of cyclopentadiene anddicyclopentadiene in the presence of an acetylenic reactant as shownbelow in Scheme 3:

where in “g” is an integer from 0 to 5, R^(F1) and R^(F4) are aspreviously defined for structure (F) Examples of bicyclic and polycyclicolefins thus include, without limitation, dicyclopentadiene (DCPD);trimer and other higher order oligomers of cyclopentadiene includingwithout limitation tricyclopentadiene (cyclopentadiene trimer),cyclopentadiene tetramer, and cyclopentadiene pentamer;ethylidenenorbornene; dicyclohexadiene; norbornene;5-methyl-2-norbomene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene;5-acetylnorbomene; 5-methoxycarbonylnorbornene;5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene;cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo,endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene;endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbomadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyltetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;and the like, and their structural isomers, stereoisomers, and mixturesthereof. Additional examples of bicyclic and polycyclic olefins include,without limitation, C₂-C₁₂ hydrocarbyl substituted norbornenes such as5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbomene,5-decyl-2-norbomene, 5-dodecyl-2-norbomene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene,5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons.Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one ormore (typically 2 to 12) heteroatoms such as O, N, S, or P. For example,crown ether cyclic olefins may include numerous O heteroatoms throughoutthe cycle, and these are within the scope of the disclosure. Inaddition, preferred cyclic olefins are C₅ to C₂₄ hydrocarbons thatcontain one or more (typically 2 or 3) olefins. For example, the cyclicolefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefinsinclude without limitation cyclooctene, cyclododecene, and(c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings.For example, the cyclic olefin may be mono-, di-, or tri-cyclic. Whenthe cyclic olefin comprises more than one ring, the rings may or may notbe fused. Preferred examples of cyclic olefins that comprise multiplerings include norbornene, dicyclopentadiene, tricyclopentadiene, and5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted, for example, a C₅ to C₂₄cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with non-hydrogen substituents. Suitablenon-hydrogen substituents may be chosen from the substituents describedhereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of thehydrogens are replaced with functional groups, are within the scope ofthe disclosure. Suitable functional groups may be chosen from thefunctional groups described hereinabove. For example, a cyclic olefinfunctionalized with an alcohol group may be used to prepare a telechelicpolymer comprising pendent alcohol groups. Functional groups on thecyclic olefin may be protected in cases where the functional groupinterferes with the metathesis catalyst, and any of the protectinggroups commonly used in the art may be employed. Acceptable protectinggroups may be found, for example, in Greene et al., Protective Groups inOrganic Synthesis, 3rd Ed. (New York: Wiley, 1999). A non-limiting listof protecting groups includes: (for alcohols) acetyl, benzoyl, benzyl,β-Methoxyethoxymethyl ether (MEM), Dimethoxytrityl,[bis-(4-methoxyphenyl)phenylmethyl] (DMT), methoxymethyl ether (MOM),methoxytrityl [(4-methoxyphenyl)diphenylmethyl, MMT), p-methoxybenzylether (PMB), methylthiomethyl ether, pivaloyl (Piv), tetrahydropyranyl(THP), tetrahydrofuran (THF), trityl (triphenylmethyl, Tr), silyl ethers(most popular ones include trimethylsilyl (TMS), tert-butyldimethylsilyl(TBDMS), tri-iso-propylsilyloxymethyl (TOM), and triisopropylsilyl(TIPS) ethers, (for amines) tert-butyloxycarbonyl glycine,carbobenzyloxy (Cbz) group, p-methoxybenzyl carbonyl (Moz or MeOZ)group, tert-butyloxycarbonyl (BOC) group, 9-fluorenylmethyloxycarbonyl(FMOC) group, acetyl (Ac) group, benzoyl (Bz) group, benzyl (Bn),carbamate group, p-methoxybenzyl (PMB), 3,4-dimethoxybenzyl (DMPM),p-methoxyphenyl (PMP) group, tosyl (Ts) group, (for carbonyls) acetalsand ketals, acylals, dithianes, (for carboxylic acids) methyl esters,benzyl esters, tert-butyl esters, esters of 2,6-disubstituted phenols(e.g. 2,6-dimethylphenol, 2,6-diisopropylphenol,2,6-di-tert-butylphenol), silyl esters, orthoesters, oxazoline, (forphosphate) 2-cyanoethyl, and methyl. In the specific case of arginine(Arg) side chains, protection is important because of the propensity ofthe basic quanidinium group to produce side reactions. In casesdescribed herein, effective protective groups include2,2,5,7,8-pentamethylchroman (Pmc),2,2,4,6,7-pentamethyldihydrobenzofurane (Pbf) and1,2-dimethylindole-3-sulfonyl (MIS) groups.

Examples of functionalized cyclic olefins include without limitation2-hydroxymethyl-5-norbornene,2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cydecanol,5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the methods disclosed herein. Additionally,cyclic olefins incorporating any combination of the abovementionedfeatures (i.e., heteroatoms, substituents, multiple olefins, multiplerings) are suitable for the invention(s) disclosed herein.

The cyclic olefins useful in the methods disclosed herein may bestrained or unstrained. It will be appreciated that the amount of ringstrain varies for each cyclic olefin compound, and depends upon a numberof factors including the size of the ring, the presence and identity ofsubstituents, and the presence of multiple rings. Ring strain is onefactor in determining the reactivity of a molecule towards ring-openingolefin metathesis reactions. Highly strained cyclic olefins, such ascertain bicyclic compounds, readily undergo ring opening reactions witholefin metathesis catalysts. Less strained cyclic olefins, such ascertain unsubstituted hydrocarbon monocyclic olefins, are generally lessreactive. In some cases, ring opening reactions of relatively unstrained(and therefore relatively unreactive) cyclic olefins may become possiblewhen performed in the presence of the olefinic compounds disclosedherein.

A plurality of cyclic olefins may be used with the present disclosure toprepare metathesis polymers. For example, two cyclic olefins selectedfrom the cyclic olefins described hereinabove may be employed in orderto form metathesis products that incorporate both cyclic olefins. Wheretwo or more cyclic olefins are used, one example of a second cyclicolefin is a cyclic alkenol, i.e., a C₅-C₂₄ cyclic hydrocarbon wherein atleast one of the hydrogen substituents is replaced with an alcohol orprotected alcohol moiety to yield a functionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when atleast one of the cyclic olefins is functionalized, allows for furthercontrol over the positioning of functional groups within the products.For example, the density of cross-linking points can be controlled inpolymers and macromonomers prepared using the methods disclosed herein.Control over the quantity and density of substituents and functionalgroups also allows for control over the physical properties (e.g.,melting point, tensile strength, glass transition temperature, etc.) ofthe products. Control over these and other properties is possible forreactions using only a single cyclic olefin, but it will be appreciatedthat the use of a plurality of cyclic olefins further enhances the rangeof possible metathesis products and polymers formed.

More preferred cyclic olefins include dicyclopentadiene;tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbomene;5-ethyl-2-norbornene; 5-isobutyl-2-norbornene;5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbomene;5-acetylnorbornene; 5-methoxycarbonylnorbornene;5-ethoxycarbonyl-1-norbornene; 5-methyl-5-methoxy-carbonylnorbornene;5-cyanonorbomene; 5,5,6-trimethyl-2-norbomene; cyclo-hexenylnorbornene;endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene;endo, exo-5-6-dimethoxycarbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene;norbornadiene; tricycloundecene; tetracyclododecene;8-methyltetracyclododecene; 8-ethyl-tetracyclododecene;8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene;8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene;higher order oligomers of cyclopentadiene such as cyclopentadienetetramer, cyclopentadiene pentamer, and the like; and C₂-C₁₂ hydrocarbylsubstituted norbornenes such as 5-butyl-2-norbomene;5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene;5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbomene;5-isopropenyl-2-norbomene; 5-propenyl-2-norbomene; and5-butenyl-2-norbornene, and the like. Even more preferred cyclic olefinsinclude dicyclopentadiene, tricyclopentadiene, and higher orderoligomers of cyclopentadiene, such as cyclopentadiene tetramer,cyclopentadiene pentamer, and the like, tetracyclododecene, norbornene,and C₂-C₁₂ hydrocarbyl substituted norbornenes, such as5-butyl-2-norbornene, 5-hexyl-2-norbomene, 5-octyl-2-norbornene,5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropenyl-2-norbomene,5-propenyl-2-norbomene, 5-butenyl-2-norbornene, and the like.

In certain embodiments, each of these Structures A-F may furthercomprise pendant substituents that are capable of crosslinking with oneanother or added crosslinking agents. For example, R^(A1), R^(A2),R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), R^(B6), R^(C1), R^(C2), R^(C3),R^(C4), R^(C5), R^(C6), R^(D1), R^(D2), R^(D3), R^(D4), R^(E1), R^(E2),R^(E3), R^(E4), R^(E5), R^(E6), R^(E7), R^(E8), R^(F1), R^(F2), R^(F3),and R^(F4) may independently represent pendant hydrocarbyl chainscontaining olefinic or acetylenic bonds capable of crosslinking withthemselves or other unsaturated moieties under metathesis conditions.Additionally, within Structures A-F, at least one pair of substituents,R^(B1) and R^(B2), R^(B3) and R^(B4), and R^(B5) and R^(B6), R^(C1) andR^(C2), R^(C5) and R^(C6), R^(D2) and R^(D3), R^(E5) and R^(E6), R^(E7)and R^(E8), R^(F1) and R^(F2), and R^(F3) and R^(F4), can together forman optionally substituted exocyclic double bond, for example/═CH(C₁₋₆-Fn). This concept is specifically exemplified in the Examples,where a compound of Structure (F), where a is a single bond, g is 0,R^(F1)═R^(F2)═H, and R^(F3) and R^(F4) together form /═CH(ethyl) isreacted with oligomers of cyclooctadiene.

When considering alternative olefinic precursors in the present methods,more preferred precursors may be those which, which when incorporatedinto polyacetylene polymers or copolymers, modify the electrical orphysical character of the resulting polymer. One general class of suchprecursors are substituted annulenes and annulynes, for example[18]annulene-1,4;7,10;13,16-trisulfide. When co-polymerized withacetylene, this precursor can form a block co-polymer as shown here:

Substituted analogs of these trisulfides, as described below can also beused to provide corresponding substitutedpoly(thienylvinylene)-containing polymers or copolymers. For example,the 2,3,8,9,14,15-hexaoctyl derivative of[18]annulene-1,4;7,10;13,16-trisulfide is described in Horie, et al.,“Poly(thienylvinylene) prepared by ring-opening metathesispolymerization: Performance as a donor in bulk heterojunction organicphotovoltaic devices,” Polymer 51 (2010) 1541-1547, which isincorporated by reference herein for all purposes

In certain embodiments, the unsaturated organic precursor comprises apurely hydrocarbon compound having a structure:

or a mixture thereof, wherein Ra, R_(b), R_(c), R_(d), R_(e), and R_(f)are independently H or alkyl (preferably C₁₋₂₀ alkyl, more preferablyC₁₋₁₀ alkyl).

The unsaturated organic precursor may also comprise a hydrocarboncompound having a dicyclopentadiene structure, for example:

wherein Ra, R_(b), R_(c), R_(d), R_(e), and R_(f) are independently H oralkyl (preferably C₁₋₂₀ alkyl, more preferably C₁₋₁₀ alkyl). One suchpolymer resulting from such precursors comprises units having astructure:

See FIG. 3A.

These hydrocarbon precursors are particularly attractive, for example,when the final polymerized product or article derived therefrom is to besubject to aggressive chemical conditions. For example, patternedproducts or article derived therefrom prepared from dicyclopentadienestructures are particularly effective in resisting aqueous HF, makingthem particularly attractive for use as etching masks in semi-conductoror other electronic processing. It is believe that the term “resistantto aqueous HF” carries a practical connotation understood by thoseskilled in the art; i.e., the patterned polymer layer is sufficientlyrobust as to withstand HF (or to slow the diffusion of fluoride ionsfrom the protected surface) for a time sufficient to be practicallyuseful in etch-processing or the polymer layer is not dissolved to ameaningful extent or the crosslinked polymer matrix is able to slow thediffusion of the HF (and fluoride ions) to protect the surface fromthese reactive species. Aqueous HF itself may be also characterized byits concentration, and in various embodiments, the concentration may be5, 10, 15, 20, 25, 30, 35, 40, 45, or 48 wt %. For examples, inexperiments using such compositions of the present disclosure, it waspossible to selectively etch 30 micron posts in silicon dioxide (glass)in less than minute. Unless otherwise stated, the term “resistant toaqueous HF” is defined as being able to withstand exposure to aqueous HFat room temperatures (i.e., ca. 20-25° C.) for a period of 1 hourwithout measurable peeling from the substrate. Where specified, the termmay also be defined in this way in terms of longer (e.g., 2, 3, 4, 5, 6,12, 24, 48, or 96 hours) or shorter (e.g., 1, 5, 10, 20, 30, 40, or 50minutes) exposure times. Such materials are also extremely tough anddurable, and may be used in applications in bullet-proof vests andcarbon fiber composites (e.g., as used in wind turbine blades)

In other embodiments, the unsaturated polymerizable material matrix mayinclude mono-, di-, or polyfunctionalized cyclic or alicyclic alkenes oralkynes; i.e., which include functional groups, including for example,alcohols, amines, amides, carboxylic acids and esters, phosphines,phosphonates, sulfonates or the like. Optionally substitutedbicyclo[2.2.1]hept-5-ene-2,3,dicarboxylic acid diesters,7-oxa-bicyclo[2.2.1]hept-5-ene-2,3,dicarboxylic acid diesters,4-oxa-tricyclo[5.2.1.0^(2,6)] dec-8-ene-3,5-diones, 4,10-dioxa-tricyclo[5.2.1.0^(2,6)] dec-8-ene-3,5-diones,4-aza-tricyclo[5.2.1.0^(2,6)] dec-8-ene-3,5-diones,10-oxa-4-aza-tricyclo[5.2.1.0^(2,6)] dec-8-ene-3,5-diones, or simpledi-substituted alkenes, including bisphosphines may provide goodresults. In certain embodiments, these functionalized alkenes includethose having structures such as:

wherein

wherein

Z is —O— or C(R_(a))(R_(b));

R^(P) is independently H; or C₁₋₆ alkyl optionally substituted at theterminus with —N(R_(a))(R_(b)), —O—R_(a), —C(O)O—R_(a), —OC(O)—(C₁₋₆alkyl), or —OC(O)—(C₆₋₁₀ aryl); or an optionally protected sequence of 3to 10 amino acids (preferably including R-G-D orarginine-glycine-aspartic acid);

W is independently —N(R_(a))(R_(b)), —O—R_(a), or —C(O)O—R_(a),—P(O)(OR_(a))₂, —SO₂(OR_(a)), or SO₃—;

R_(a) and R_(b) are independently H or C₁₋₆ alkyl;

the C₆₋₁₀ aryl is optionally substituted with 1, 2, 3, 4, or 5optionally protected hydroxyl groups (the protected hydroxyl groupspreferably being benzyl); and

n is independently 1, 2, 3, 4, 5, or 6.

Non-limiting examples of such functionalized materials include:

where Bn is benzyl, tBu is tert-butyl, and Pbf is2,2,4,6,7-pentamethyldihydrobenzofuran. Other protecting groups may alsobe employed.

Incorporation of such functional groups provides for furtherfunctionalization of the pre-polymerized or polymerized compositions,thereby greatly expanding the utility options available for suchcompositions. Such functional groups, then, can be used as linkingpoints for the additional of other materials, including, for example,natural or synthetic amino acid sequences. In certain embodiments, R^(P)can be further functionalized to include:

Polymerized products (either 2-dimensional optionally patterned coatingsor optionally patterned 3-dimensional structures) prepared from thepre-polymerized compositions may be useful as scaffolds for drugdelivery or tissue regeneration. Films or articles comprising pendantoptionally protected sequence of 3 to 10 amino acids (preferablyincluding R-G-D or arginine-glycine-aspartic acid) are known to beuseful in tissue regeneration applications and the present inventivecompositions and methods provide convenient routes to these materials

Building upon this concept of incorporating functionalized materialsinto or pendant to polymer matrices (either films or 3-dimensionalarticles) derived from photosensitive polymerizable matrices, thepresent inventors have also discovered that it is possible toincorporate catalytic organometallic materials into such matrices. Inparticular, the present invention(s) contemplates photosensitivecompositions comprising a Fischer-type carbene ruthenium metathesiscatalyst admixed or dissolved within a polymerizable material matrixcomprising at least one unsaturated organic precursor and at least oneunsaturated tethered organometallic precursor, or ligand capable ofcoordinating to form an organometallic precursor (e.g., vinylbipyridine, bisphosphines, and carbene precursors) each organic andorganometallic precursor having at least one alkene or one alkyne bond.

As used herein, the term “unsaturated tethered organometallic precursor”is defined as referring to organometallic complex having a pendantalkene or alkyne group capable of being incorporated into thepolymerized matrix. This concept of tethering organometallic materials,including catalytic materials is well understood in chemistry, as suchtethering methods are frequently used to immobilize homogenous catalystsonto stationary matrices (e.g., silica or alumina). By “tethered” or“tethering group,” it is appreciated by the person of skill in the artthat this refers to linking groups, for example hydrocarbylene linkinggroup such as an alkylene, substituted alkylene, heteroalkylene,substituted heteroalkene, arylene, substituted arylene, heteroarylene,or substituted heteroarylene linkage, including alkylene, arylene,amido, amino, or carboxylato. The specific nature of the linking groupis not believed to be necessarily limiting, provided the group containsa reactive alkene or alkyne group capable of being incorporated into thepolymerized matrix.

In some embodiments, the organometallic moiety comprises a Group 3 toGroup 12 transition metal, preferably Fe, Co, Ni, Ti, Al, Cu, Zn, Ru,Rh, Ag, Ir, Pt, Au, or Hg. In preferred embodiments, the organometallicmoiety comprises Fe, Co, Ni, Ru, Rh, Ag, Ir, Pt, or Au. Theorganometallic moieties may be attached by or contain monodentate,bidentate, or polydentate ligands, for example cyclopentadienyls,imidazoline (or their carbene precursors), phosphines, polyamines,polycarboxylates, nitrogen macrocycles (e.g., porphyrins or corroles),provided these ligands contain the pendant alkene or alkyne groupcapable of being incorporated into the polymerized matrix. Non-limitingexamples of this concept include:

Representative chemistry of the polymerized product into which such anorganometallic was incorporated is illustrated in U.S. patentapplication Ser. No. 14/505,824.

In certain embodiments, the organometallic moiety is chosen to becapable of catalyzing the oxidation or reduction of an organic substrateunder oxidizing or reducing conditions. The terms “oxidizing or reducingconditions” are likewise generally understood by chemists skilled in theart, and include those conditions comprising the presence of oxidizing(oxygen, peroxides, etc.) or reducing (hydrogen, hydrides, etc.) agents.Such oxidation reactions include, but are not limited to, oxidations ofalkenes or alkynes to form alcohols, aldehydes, carboxylic acids oresters, ethers, or ketones, or the addition of hydrogen-halides orsilanes across unsaturates. Such oxidation reactions include, but arenot limited to, reduction of alkenes to alkanes and reduction of alkynesto alkenes or alkanes. Certain of these organometallic moieties may beused as pendant metathesis or cross-coupling catalysts or for splittingwater.

Metatheses Reactions

The metathesis reactions contemplated by the present disclosure includeRing-Opening Metathesis Polymerization (ROMP), Ring-Closing Metathesis(RCM), and Cross Metathesis (CM). While often described in termsof“olefin metathesis,” it should also be understood that both olefinicand acetylenic bonds can participate in such reactions, and so as usedherein, the term “olefin metathesis” is to be interpreted as involvingthe redistribution of olefinic or acetylenic bonds. Each of these typesof reactions is well known to those skilled in the relevant art in thiscapacity.

In those contemplated embodiment related to photoresists (to bedescribed further infra), the descriptions are generally provided interms of selective polymerizations, for example by ROMP orcross-metathesis, so as to provide spatially specific regions ofcross-linked polymers. But it should also be appreciated that thisspatial and temporal selectivity available by the photoactivatedcatalysts may also be applied to change the solubility properties of theirradiated region without crosslinking—for example by only partialreaction of the precursors, cross metathesis of an olefinic precursorwith a polymer, or through depolymerization.

Photosensitive Compositions, Including Photoresists

As should be appreciated by the descriptions herein, one of the severalfeatures of the present disclosure is the ability to spatially andtemporally control the catalytic activities of the systems withremarkable precision, owing to the high contrast in activity between theirradiated and unirradiated catalysts. The high activities of theirradiated catalysts allows for good activity, even at low embeddedcatalyst concentrations. In some embodiments, the Fischer-type carbeneruthenium metathesis catalyst is present at a concentration in a rangeof from about 0.001% to about 5% by weight, relative to the weight ofthe entire composition. This concentration range depends on thereactivities of the catalyst and the polymerizable material precursors,the desired handling conditions, and the desired rates ofpolymerization. In certain other embodiments, ruthenium carbenemetathesis catalyst is present at a concentration in a range of fromabout 0.001% to about 0.01%, from about 0.01% to about 0.1%, from about0.1% to about 1%, from about 1% to about 2%, from about 2% to about 3%,from about 3% to about 4%, from about 4% to about 5%, or a combinationthereof, all by weight, relative to the weight of the entirecomposition. The systems also allow for higher concentrations, forexample up to about 10 or 15% by weight, relative to the weight of theentire composition, but here cost begins to become dissuasive for mostpractical applications.

As described above, the methods of the present disclosure also considerthat the Fischer-type carbene ruthenium metathesis catalyst, asdescribed herein, may be dissolved in a solvent in the presence of atleast one unsaturated organic precursor or are admixed or dissolved inat least one unsaturated organic precursor. In the circumstances wherethe user contemplates the use of these compositions as photoresists, theFischer-type catalyst may be added to the organic precursor directly orgenerated in situ as described elsewhere herein. This in situ generationof the catalyst may involve providing a catalyst containing aSchrock-type carbene, which is subsequently quenched to form theFischer-type carbene catalyst. If so, the generation of the catalyst maybe accompanied by partial polymerization or cross-linking of theoriginally added organic precursor, and the intermediate viscosity ofthis partial polymerized or cross-linked composition may be controlledby the time before quenching. Raising the viscosity of thephotosensitive compositions provides several advantages, includingimproving the oxidative stability of the otherwise potentiallyair-sensitive catalysts. The raised viscosity also controls thediffusion length of the active catalyst species through the composition,which in turn can improve the resolution of the lithographically definedstructures.

In some embodiments, it is convenient to use a non-reactive solvent (lowboiling solvents may be preferred, such as methylene chloride,tetrahydrofuran, diethyl ether, toluene, etc.) to provide and maintainlower initial viscosities, so as to allow for more efficient intimatemixing of the catalyst within the total composition. In the case of thephenanthroline-ligated catalysts derivatives described herein, use ofmore reactive solvents, including water, acetonitrile, and chloroform,may be tolerable. Once the catalyst is intimately distributed within thecomposition, the non-reactive solvent may be conveniently removed, forexample under vacuum or with heat. In some cases, once the Fischer-typecatalyst is added or prepared, additional or different organic precursormay be added to dilute the catalyst further. The viscosity of the final,unexposed product may be adjusted by the type and amount of theconstituents. For example, in some embodiments, the viscosity is suchthat the composition is suitable for spin-coating, dip coating, orspraying. In other embodiments, the photosensitive composition can havethe form of a gelled, solid, or semi-solid film. In various independentembodiments, the viscosity of the composition, at the contemplatedtemperature of application (preferably ambient room temperature) is in arange of from about 1 cSt to about 10 cSt, from about 10 cSt to about 50cSt, from about 50 cSt to about 100 cSt, from about 100 cSt to about 250cSt, from about 250 cSt to about 500 cSt, from about 500 cSt to about1000 cSt, from about 1000 cSt to about 2000 cSt, from about 2000 cSt toabout 5000 cSt, or higher. Higher viscosities appear provide increasedoxidative stability of the ruthenium carbene catalysts.

Part of the challenge in developing an olefin metathesis-basedphotoresist is achieving a stark contrast between the reactivity of thecatalyst in the light and the dark. Additionally, the requirements ofambient stability and processability present barriers to the industrialimplementation of transition metal based photocatalysts. In the presentdisclosure, certain embodiments provide that a standard quenchingprocedure for ROMP or cross-metathesis reactions generates a latentphotoactive catalyst. This serendipitous discovery allows for the facilesynthesis of a new family of photocurable materials. The addition ofsubstituted vinyl ethers is a widely employed method of quenching ROMPor cross-metathesis reactions. The regioselective formation of vinylether complexes, for example, is extremely rapid and irreversible undercertain conditions, leading to the use of vinyl ether “trapping” as atool for determining catalyst initiation rates. The resultant rutheniumFischer-type carbenes are generally considered to be unreactive. Whilenot intending to be bound by the correctness or incorrectness of anyparticular theory, it appears that quenching a living ROMP reactionyields a methylene-terminated polymer chain and a presumably 14-electronruthenium vinyl ether. While the phosphine or pyridine ligands typicallyfound on ruthenium ROMP catalysts could in principle re-coordinate tothe quenched complex, the statistical likelihood of this is extremelylow considering the concentration and stoichiometry of typical ROMPreactions. In addition, the air-sensitivity of the ruthenium vinyl ethercomplexes aids in the quenching process, through almost immediatedecomposition of the alkylidene species. A typical quenching procedureutilizes excess vinyl ether and immediate precipitation of the polymerto remove the catalyst. Interestingly, the addition of bipyridineligands, appears to reduce the nascent reactivity of these catalystseven further, while allowing highly efficient photoactivation, such thatthe metathesis reactivity is only unleashed by irradiation with light.This enables moderate heating to be applied as part of the patterningprocess, enabling pre- or post-exposure baking steps to be implemented.

The photosensitive compositions, including photoresists, mayadditionally comprise other materials, so long as their presence doesnot interfere with the ability of the photoactivated catalysts to effectthe metathesis reactions under irradiation conditions. For example,these compositions, including photoresists, may contain colorants,surfactants, and stabilizers, as well as functional particles including,for example, nanostructures (including carbon and inorganic nanotubes),magnetic materials (e.g., ferrites), and quantum dots.

Methods of Patterning a Polymer on a Substrate

Embodiments of the present disclosure also provide methods of providingpatterned polymer layers using the Fischer-type carbene photocatalysts,which may be described as PhotoLithographic Olefin MetathesisPolymerization (PLOMP). In this procedure, a latent metathesis catalystis activated by light to react with the olefins in the surroundingenvironment, providing for the development of a negative tone resist byusing the photocatalyst to polymerize, crosslink, or both polymerize andcrosslink a difunctional ROMP monomer or other unsaturated precursorwithin a polymerizable material matrix of linear polymer or polymerprecursor. In principle, a positive tone resist can also be developed,by using light-triggered secondary metathesis events to increase thesolubility of the irradiated regions. This can be considered a“chemically amplified” resist, in that the photoactive species is acatalyst for the crosslinking of the polymer matrix. The versatility ofthese ruthenium-mediated olefin metathesis reactions can now be utilizedto photopattern a variety of functional materials via PLOMP, advancingthe field of photoinitiated olefin metathesis from a curiosity tomaterials science applicable to mass microfabrication.

Some embodiments provide methods of patterning a polymeric image on asubstrate, each method comprising;

(a) depositing a layer of photosensitive composition of any one of thecompositions described herein on the substrate;

(b) irradiating a portion of the layer of photosensitive compositionwith a light having appropriate wavelength(s), as described elsewhereherein, thereby providing a patterned layer of polymerized andunpolymerized regions. Certain other embodiments further compriseremoving the unpolymerized region of the pattern.

In principle, the substrates can comprise any metallic or non-metallic;organic or inorganic; conductive, semi-conductive, or non-conductivematerial, or any combination thereof. Even so, it is contemplated thatthese patterned polymer layers will find utility in electronicapplications including those where semiconductor wafers comprisingsilicon, GaAs, and InP. One of the many advantages of these inventivesystems, certainly over many commercial resists, is the ability tomaintain surface adhesion to the native oxide surfaces of siliconwafers, for example, without any etching or surface derivatization. Bycontrast, many commercial photoresists require HF etching of the oxideand/or surface derivatization with reactive molecules such ashexamethyldisilazane. In this respect, the presently describedphotosensitive systems offer a safer and more versatile alternative, asthe polymer composition can be easily tuned to modulate adhesion. Forexamples, in the examples described herein, the poly(COD) resist batchesshowed excellent adhesion to silicon coupons, which were first cleanedwith piranha. Additionally, the PLOMP resists do not requirepost-exposure baking to develop. Currently, ruthenium-mediated ROMP isemployed in a number of industrial scale applications, includinghigh-modulus resins and extremely chemically resistant materials. PLOMPcan provide UV-curable and patternable coatings with these desiredmaterials properties. Finally, the ability to generate many batches ofresist in a single workday enables rapid prototyping for futuredevelopment.

In some embodiments, the patterned polymers may be processed to formsingle layer or multilayer polymer structures. In multilayer structures,each layer may be the same or different than any other of the depositedlayer, and may be individually patterned as described herein. Similarly,each layer may be interleaved with intermediately deposited metal, metaloxide, or other material layer. These interlayers may be deposited forexample by sputtering, or other chemical or vapor deposition technique,provided the processing of these interlayers does not adversely affectthe quality of the patterned layers of deposited polymers.

The photosensitive compositions may be deposited by spin coating, dipcoating, or spray coating, or alternatively, depending on the physicalform of the photosensitive composition, may be deposited by laminating agelled or solid film on the substrate.

The photosensitive compositions may be irradiated by any variety ofmethods known in the art. In certain embodiments, patterning may beachieved by photolithography, using a positive or negative imagephotomask. In other embodiments, patterning may be achieved byinterference lithography (i.e., using a diffraction grating). In otherembodiments, patterning may be achieved by proximity fieldnanopatterning. In still other embodiments, patterning may be achievedby diffraction gradient lithography. In still other embodiments,patterning may be used by a direct laser writing application of light,such as by multi-photon lithography. Additional embodiments provide thatthe patterning may be accomplished by nanoimprint lithography. Further,the patterning may be accomplished by inkjet 3D printing,stereolithography and the digital micromirror array variation ofstereolithography (commonly referred to as digital light projection(DLP). These inventive compositions are especially amenable to preparingstructures using stereolithographic methods, for example includingdigital light projection (DLP) (see Examples). In some embodiments, thephotosensitive compositions may be processed as bulk structures, forexample using vat polymerization, wherein the photopolymer is cureddirectly onto a translated or rotated substrate, and the irradiation ispatterned via stereolithography, holography, or digital light projection(DLP). “Stereolithography” is a method and apparatus for making solidobjects by successively “printing” thin layers of a curable material,e.g., a UV curable material, one on top of the other. A programmedmovable spot beam of UV light shining on a surface or layer of UVcurable liquid is used to form a solid cross-section of the object atthe surface of the liquid. The object is then moved, in a programmedmanner, away from the liquid surface by the thickness of one layer, andthe next cross-section is then formed and adhered to the immediatelypreceding layer defining the object. This process is continued until theentire object is formed. Such methods are summarized and described inU.S. Pat. No. 5,571,471, which is incorporated by reference herein inits entirety for its teaching of such methods.

The Fischer-type carbene ruthenium metathesis catalysts can be activatedusing light having at least one wavelength in a range of from about 300to about 500 nm. Additional embodiments provide that the light comprisesat least one wavelength in a range of from about 300 to about 320 nm,from about 320 to about 340 nm, from about 340 to about 360 nm, fromabout 360 to about 380 nm, from about 380 to about 400 nm, from about400 to about 420 nm, from about 420 to about 440 nm, from about 440 toabout 460 nm, from about 460 to about 480 nm, from about 480 to about5000 nm, or a combination thereof. In other preferred embodiments, thiswavelength is in a range of from about 380 to about 420 nm. As describedabove, the intensity of this at least wavelength is in a range of about1 mW/cm² to 10 W/cm², preferably about 10 mW/cm² to 200 mW/cm². Inspecific embodiments, the intensity of the photoactivating source may bein a range of from about 1 mW/cm² to about 5 mW/cm², from about 5 mW/cm²to about 10 mW/cm², from about 10 mW/cm² to about 50 mW/cm², from about50 mW/cm² to about 100 mW/cm², from about 100 mW/cm² to about 200mW/cm², from about 200 mW/cm² to about 300 mW/cm², from about 300 mW/cm²to about 400 mW/cm², from about 400 mW/cm² to about 500 mW/cm², fromabout 500 mW/cm² to about 1 W/cm², from about 1 W/cm² to about 5 W/cm²,from about 5 W/cm² to about 10 W/cm², or any combination of two or moreof these ranges. In certain aspects, the catalysts can be activatedusing 2- or 3-photon energy sources at 700 to 800 nm, more specificallyusing a 790 nm laser. This two-photon energy is equivalent to 395 nm;the 3-photon energy is equivalent to about 263 nm).

The dimensions of the resulting features of the polymerized structuresare, in part, dictated by the wavelength of the irradiating light, themethod of irradiation, and the character of the photosensitivecompositions. Higher viscosities and the optional presence of additionalquenchants may usefully minimize diffusion of the catalyst in thecomposition, so as to provide for better resolution. In certainembodiments, the polymerized polymer exhibits features (e.g., channels,ridges, holes, or posts) having dimensions on the millimeter scale(e.g., from about 1 mm to about 10 mm, from about 10 mm to about 50 mm,from about 50 mm to about 100 mm, from about 100 mm to about 500 mm,from about 500 mm to about 1000 mm, or a combination thereof), themicron scale (e.g., from about 1 micron to about 10 microns, from about10 microns to about 50 microns, from about 50 microns to about 100microns, from about 100 microns to about 500 microns, from about 500microns to about 1000 microns, or a combination thereof), or thenanometer scale (e.g., from about 1 nm to about 10 nm, from about 10 nmto about 50 nm, from about 50 nm to about 100 nm, from about 100 toabout 200 nm, from about 200 to about 300 nm, from about 300 to about400 nm, from about 400 to about 500 nm, from about 500 to about 600 nm,from about 600 to about 700 nm, from about 700 to about 800 nm, or acombination thereof. Interference or diffraction gradient lithographymay provide for polymer layers having continuous or discontinuousthicknesses.

The methods and derived polymer products may generally serve as masks ortemplates for chemical etching processes. Polymers made by theseprocesses are qualitatively stable to dichloromethane, isopropanol,acetone, 2.5 M hydrochloric acid, and concentrated sulfuric acid. afterbeing submerged for approximately 24 hours.

Three-Dimensional Structures

The present disclosure(s) also provides compositions and methodssuitable for making 3-dimensional structures comprising a plurality ofpolymer layers and 3-dimensional patterns. The ability to providespecifically dimensioned patterns makes these structures particularlyuseful, for example, in 3-dimensional photonic or chemochromic devices.

In certain embodiments, such structures are prepared by methodscomprising:

(a) depositing at least two layers of a polymerizable materialcomposition having at least one alkene or alkyne capable of undergoing ametathesis polymerization or crosslinking reaction and an appropriatephotocatalyst, at least one of these layers containing the rutheniumbipyridine complexes described herein acting in this capacity, thedeposition forming a stacked assembly;

(b) irradiating at least a portion of the stacked assembly with light,such that light penetrates and irradiates at least two layers of thestacked assembly, under conditions sufficient to polymerize or crosslinkat least portions of adjacent layers of the stacked assembly

In related embodiments, the portions of the assembly not reacted may besubsequently removed.

These layers of polymerizable materials generally, but not necessarily,comprise mainly polymers, with the additional presence of small amountsof polymerizable precursors or crosslinkers. That is, each layer maycomprise at least 50%, 60%, 70%, 80%, 90%, 95%, or 98% by weight ofpreformed polymer, the weight percentage based on the total weight ofthe layers of a polymerizable material.

In some embodiments, one or more of the at least two layers of apolymerizable material may contain residual ruthenium metathesiscatalyst that was used to prepare that particular layer. That is, thatlayer may have already been derived from a ROMP-type catalysissynthesis, and have residual catalyst contained therein. Alternatively,additional or new ruthenium metathesis catalyst may be admixed ordissolved within a pre-prepared layer of a polymerizable material bydissolving it in the presence of a solvent (as described herein) orincorporating the catalyst into a solvent swelled.

Such layer or layers may also contain residual polymer precursor fromthe original (incomplete) polymerization or contain residual lessreactive polymer precursors. Alternatively, the layer may have hadadditional polymerizable or crosslinkable materials added to it, forexample by dissolving or swelling the layer in the presence of theadditional polymerizable or crosslinkable material. Such residualprecursors are akin to those described herein. Other chemicalcross-linkers are known in the art.

The stacked assembly may be formed to comprise adjacent layers havingmaterials of similar composition. Alternatively, adjacent layers may becompositionally different. Or the stacked assembly may comprise acombination of adjacent layers being compositionally the same anddifferent. In preferred embodiments, each layer of the stacked assemblycomprises a pre-formed polymer having different chemistries from otherpre-formed polymer(s) in the other layer(s). Individual layers withinthe stacked assembly may have thickness of any practical dimension, butparticular embodiments include those where the thickness of each layeris independently on the millimeter scale (e.g., from about 1 mm to about10 mm, from about 10 mm to about 50 mm, from about 50 mm to about 100mm, from about 100 mm to about 500 mm, from about 500 mm to about 1000mm, or a combination thereof), the micron scale (e.g., from about 1micron to about 10 microns, from about 10 microns to about 50 microns,from about 50 microns to about 100 microns, from about 100 microns toabout 500 microns, from about 500 microns to about 1000 microns, or acombination thereof), or the nanometer scale. In the latter case, thelayers may be independently in a range of from about 50 to about 100 nm,from about 100 to about 200 nm, from about 200 to about 300 nm, fromabout 300 to about 400 nm, from about 400 to about 500 nm, from about500 to about 600 nm, from about 600 to about 700 nm, from about 700 toabout 800 nm, from about 800 to about 900 nm, from about 900 to about1000 nm, or a combination thereof. By selecting the thickness andoptical characteristics of adjacent layers, it is possible to tune theoptics of the entire device.

In certain cases, the layers of the polymerizable material compositionsmay be deposited sequentially upon one another, or may be allowed toself-assemble to the stacked assembly when different materials are mixedtogether in a liquid. Self-assembly would appear to be a more intimateand useful way of forming such stacked structures, particularly at thenano-scale dimensions useful for photonic or chemochromic devices, butthe ability to self-assemble effectively depends on the nature of thevarious layers. For example, certain block copolymers are able toself-assemble providing lateral and vertical domains having dimensionsin a range of from about 5 to about 1500 nanometer, preferably in arange of from about 75 to about 300 nm domains. As such, layerscomprising block copolymers are useful materials to be incorporated inthese methods. Brush (graft) block, wedge-type block, and hybrid wedgeand polymer block copolymers. See FIG. 6. Such block copolymers aredescribed in copending U.S. Patent Application Publication Nos.2014/0011958, 2013/0296491, and 2013/0324666 and in Piunova, et al., J.Amer. Chem. Soc, 2013, 135 (41), pp 15609-15616, Miyake, G. M., et al.,Angewandte Chemie International Edition 2012, 51, 11246-11248,Sveinbjörnsson, B. R., et al., PNAS 2012, 109, 14332-14336, and Miyake,G. M., et al., J. Am. Chem. Soc. 2012, 134, 14249-14254, each of whichis incorporated by reference for their description of the polymers andcopolymers. These compositions are considered especially attractivematerials to be used in these methods, though the methods are notlimited to these choices of materials.

Once the stacked assembly is formed, at least a portion of it is subjectto irradiation with light, under conditions described herein, such thatlight penetrates and irradiates at least two layers of the stackedassembly, under conditions sufficient to polymerize or crosslink atleast portions of adjacent layers of the stacked assembly. Whereas theadjacent layers could be delaminated prior to irradiation, theapplication of light activates the incorporated ruthenium metathesiscatalyst to crosslink these adjacent layers to a coherent structure. Inother embodiments, the light is directed to pass through and irradiateat least a portion of all of the layers of the stacked assembly. Inother embodiments, the entire structure is irradiated with light underconditions to crosslink the entire assembly.

Whereas a stacked assembly can be irradiated in its entirety, anotherset of embodiments provide that the irradiating is done by patternedexposure of light to the stacked assembly, so as to provide athree-dimensional pattern of polymerized and unpolymerized regionsthrough the stacked assembly. Much like the compositions provide thatpatterned irradiation of planar polymer layers can give rise to nano-and micro-dimensioned patterns, for example by using a direct writingapplication of light or by interference, nanoimprint, or diffractiongradient lithography, so too can this same patterning technology be usedto form similarly dimensioned patterns in 3-dimensions. Once selectivelypolymerized or crosslinked, the unreactive portions of the structure maybe removed.

As expected, embodiments of the present disclosure include thosestructures prepared using these methods, and articles incorporatingthese structures. Photonic devices, including chemochromic sensors,solar cells, dielectric mirrors, and reflective coatings arecontemplated embodiments.

ADDITIONAL EMBODIMENTS

The following listing of embodiments in intended to complement, ratherthan displace or supersede, the previous descriptions.

Embodiment 1

A photosensitive composition comprising a ruthenium carbene metathesiscatalyst of Formula (I) or a geometric isomer thereof:

admixed within a polymerizable material matrix comprising at least oneunsaturated organic precursor, including ROMP or cross-metathesisprecursors;

wherein

X¹ and X² are independently anionic ligands;

Y is O, N—R¹, or S, preferably O; and

Q is a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or—CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, andR¹⁴ are independently hydrogen an optionally substituted hydrocarbyl;

R¹ and R² are independently hydrogen, optionally substitutedhydrocarbyl, or may be linked together to form an optionally substitutedcyclic aliphatic group;

R³ and R⁴ are independently optionally substituted hydrocarbyl; and

R⁵ and R⁶ are independently H, C₁₋₂₄alkyl, C₁₋₂₄alkoxy,C₁₋₂₄fluoroalkyl, C₁₋₂₄fluoroalkoxy, C₁₋₂₄alkylhydroxy,C₁₋₂₄alkoxyhydroxy, C₁₋₂₄fluoroalkylhydroxy(includingperfluoroalkylhydroxy), C₁₋₂₄fluoroalkoxyhydroxy, halo, cyano, nitro, orhydroxy; and

m and n are independently 1, 2, 3, or 4.

The ruthenium carbene metathesis catalyst of Formula (I) may be added asdescribed here or generated in situ as described herein. The independentX¹ and X² are anionic ligands are believed to be positioned cis withrespect to one another, though the compounds may also be present asgeometric isomers of the structure presented.

Embodiment 2

The photosensitive composition of Embodiment 1, wherein theRu═C(R¹)(Y—R²) moiety is a substituted vinyl ether carbene. In certainAspects of this Embodiment, R² is C₁₋₆ alkyl, preferably ethyl, propyl,or butyl; that is, R¹ is H, R² is C₁₋₆ alkyl, and Y is O.

Embodiment 3

The photosensitive composition of Embodiment 1 or 2, wherein Q is—CH₂—CH₂— and either R³ or R⁴, or both R³ and R⁴ are optionallysubstituted phenyl groups, optionally substituted at least in the 2, 6positions with independent C₁₋₆ alkyl groups, preferably C₃₋₆ alkylgroups which may be branched or linear, e.g., including methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl. Additionally, thephenyl groups may be optionally substituted in the 4-positions with anelectron-withdrawing or -donating group as described herein, forexample, alkyl, alkoxy, nitro, or halo.

Embodiment 4

The photosensitive composition of any one of Embodiments 1 to 3, whereinQ is —CH₂—CH₂— and R³ and R⁴ are independently mesityl or optionallysubstituted adamantyl.

Embodiment 5

The photosensitive composition of any one of Embodiments 1 to 4, whereinR⁵ and R⁶ are independently H, methyl, ethyl, propyl, butyl, methoxy,trifluoromethyl, fluoro, chloro, bromo, cyano, or nitro.

Embodiment 6

The photosensitive composition of any one of Embodiments 1 to 5, whereinthe optionally substituted 2,2′-bipyridine is substituted with R⁵ and R⁶in the 3,3′ or 4,4′ or 5,5′ or 6,6′ positions

In other Aspects of this Embodiment, one or more of R⁵ may be present inany one or more of the 3, 4, 5, or 6 positions, and R⁶ may beindependently present in any one or more of the 3′, 4′, 5′, or 6′positions

Embodiment 7

The photosensitive composition of any one of Embodiments 1 to 6, wherethe metathesis catalyst comprises a compound having a structure:

including a corresponding structure generated in situ.

Embodiment 8

The photosensitive composition of any one of Embodiments 1 to 7, whereinthe ruthenium metathesis catalyst is present at a concentration in arange of from about 0.001% to about 5% by weight, relative to the weightof the entire composition.

Embodiment 9

The photosensitive composition of any one of Embodiments 1 to 8, whereinthe ruthenium carbene catalyst, upon activation by irradiation of lightof at at least one wavelength in a range of from about 250 nm to about800 nm, preferably from about 350 nm to about 450 nm or in a range offrom about 380 to about 420 nm, can crosslink or polymerize at least oneof the unsaturated organic precursor. In other Aspects of thisEmbodiment, the light comprises at least one wavelength in a range offrom about 250 to about 300 nm, from about 300 to about 320 nm, fromabout 320 to about 340 nm, from about 340 to about 360 nm, from about360 to about 380 nm, from about 380 to about 400 nm, from about 400 toabout 420 nm, from about 420 to about 440 nm, from about 440 to about460 nm, from about 460 to about 480 nm, from about 480 to about 500 nm,from about 500 to about 600 nm, from about 600 to about 700 nm, fromabout 700 to about 800 nm, or a combination thereof.

Embodiment 10

The photosensitive composition of any one of Embodiments 1 to 9, whereinthe unsaturated organic precursor comprises one alkene, alkyne, or bothalkene and alkyne moieties and is capable of polymerizing whenmetathesized. In some Aspects of this Embodiment, the unsaturatedprecursor comprises a mono-unsaturated cyclic olefin; a monocyclicdiene; or a bicyclic or polycyclic olefin.

Embodiment 11

The photosensitive composition of any one of Embodiments 1 to 10,wherein the unsaturated organic precursor is a ROMP precursor.

Embodiment 12

The photosensitive composition of any one of Embodiments 1 to 11,wherein the unsaturated organic precursor comprises:

(a) a mono-unsaturated cyclic olefin represented by the structure (B)

wherein b is an integer generally although not necessarily in the rangeof 1 to 10, typically 1 to 5,

R^(A1) and R^(A) are independently hydrogen, hydrocarbyl (e.g., C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₅-C₃₀ aralkyl, or C₅-C₃₀ alkaryl), substitutedhydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₅-C₃₀aralkyl, or C₅-C₃₀ alkaryl), heteroatom-containing hydrocarbyl (e.g.,C₁-C₂₀ heteroalkyl, C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀aralkyl, or heteroatom-containing C₅-C₃₀ alkaryl), and substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₀ heteroaryl, heteroatom-containing C₅-C₃₀ aralkyl, orheteroatom-containing C₅-C₃₀ alkaryl) and, if substituted hydrocarbyl orsubstituted heteroatom-containing hydrocarbyl, wherein the substituentsmay be functional groups (“Fn”) such as alkene, alkyne, phosphonato,phosphoryl, phosphanyl, phosphino, sulfonato, C₁-C₂₀ alkylsulfanyl,C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfonyl, C₅-C₂₀ arylsulfonyl, C₁-C₂₀alkylsulfinyl, C₅-C₂₀ arylsulfinyl, sulfonamido, amino, amido, imino,nitro, nitroso, hydroxyl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀alkoxycarbonyl, C₅-C₂₀ aryloxycarbonyl, carboxyl, carboxylato, mercapto,formyl, C₁-C₂₀ thioester, cyano, cyanato, thiocyanato, isocyanate,thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl,siloxazanyl, boronato, boryl, or halogen, or a metal-containing ormetalloid-containing group (wherein the metal may be, for example, Sn orGe); and

R^(B1), R^(B2), R^(B3), R^(B4), R^(B5), and R^(B6) are independentlyselected from the group consisting of hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl and —(Z*)_(n)-Fn where Z* is ahydrocarbylene linking group such as an alkylene, substituted alkylene,heteroalkylene, substituted heteroalkene, arylene, substituted arylene,heteroarylene, or substituted heteroarylene linkage; and

wherein if any of the R^(B1) through R^(B6) moieties is substitutedhydrocarbyl or substituted heteroatom-containing hydrocarbyl, thesubstituents may include one or more —(Z*)_(n)-Fn groups; or

(b) a monocyclic diene represented by the structure (C)

wherein c and d are independently integers in the range of 1 to about 8,typically 2 to 4, preferably 2 (such that the reactant is acyclooctadiene);

R^(C1), R^(C2), R^(C3), R^(C4), R^(C5), and R^(C6) are defined ascorresponding to R^(B1) through R^(B6); or

(c) a bicyclic or polycyclic olefin represented by the structure (D)

wherein

R^(D1), R^(D2), R^(D3), and R^(D4) are as defined as corresponding toR^(B1) through R^(B6),

e is an integer in the range of 1 to 8 (typically 2 to 4)

f is generally 1 or 2;

T is lower alkylene or alkenylene (generally substituted orunsubstituted methyl or ethyl), CHR^(G1), C(R^(G1))₂, O, S, N—R^(G1),P—R^(G1), O═P—R^(G1), Si(R^(G1))₂, B—R^(G1), or As—R^(G1) where R^(G1)is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl, oralkoxy. Furthermore, any of the R^(D1), R^(D2), R^(D3), and R^(D4)moieties can be linked to any of the other R^(D1), R^(D2), R^(D3), andR^(D4) moieties to provide a substituted or unsubstituted alicyclicgroup containing 4 to 30 ring carbon atoms or a substituted orunsubstituted aryl group containing 6 to 18 ring carbon atoms orcombinations thereof and the linkage may include heteroatoms orfunctional groups, e.g. the linkage may include without limitation anether, ester, thioether, amino, alkylamino, imino, or anhydride moiety;or (d) a norbornenes represented by the structure (E)

wherein

R^(E1), R^(E2), R^(E3), R^(E4), R^(E5), R^(E6), R^(E7), and R^(E8) areas defined as corresponding to R^(B1) through R^(B6).

“a” represents a single bond or a double bond;

f is 1 or 2;

g is an integer from 0 to 5, and when “a” is a double bond one ofR^(E5), R^(E6) and one of R^(E7), R^(E8) is not present; or

(e) a mixture thereof.

Embodiment 13

The photosensitive composition of any one of Embodiments 1 to 11, hereinthe unsaturated organic precursor comprises a compound having astructure:

or a mixture thereof, wherein

Ra, R_(b), R_(c), R_(d), R_(e), and R_(f) are independently H or alkyl(preferably C₁₋₂₀ alkyl, more preferably C₁₋₁₀ alkyl.

Embodiment 14

The photosensitive composition of any one of Embodiments 1 to 11,wherein the unsaturated organic precursor comprises a dicyclopentadieneof structure:

wherein

Ra, R_(b), R_(c), R_(d), R_(e), and R_(f) are independently H or alkyl(preferably C₁₋₂₀ alkyl, more preferably C₁₋₁₀ alkyl.

Embodiment 15

The photosensitive composition of any one of Embodiments 1 to 14,wherein the composition has a viscosity capable of being spin coated,dip coated, or spray coated, for example with a viscosity of thecomposition, at the contemplated temperature of application (preferablyambient room temperature) is in a range of from about 1 cSt to about 10cSt, from about 10 cSt to about 50 cSt, from about 50 cSt to about 100cSt, from about 100 cSt to about 250 cSt, from about 250 cSt to about500 cSt, from about 500 cSt to about 1000 cSt, from about 1000 cSt toabout 2000 cSt, from about 2000 cSt to about 5000 cSt, or higher.

Embodiment 16

The photosensitive composition of any one of Embodiments 1 to 15,wherein the photosensitive composition is a gelled, semi-solid or solidfilm.

Photosensitive Composition Comprising Tethered Organometallic, Using anyRu-Carbene Catalyst Embodiment 17

The photosensitive composition of Embodiment 1 to 16, wherein thepolymerizable material matrix further comprises at least oneorganometallic moiety having a pendant unsaturated moiety capable ofmetathesizing with the at least one unsaturated organic precursor, thependant unsaturated moiety comprising at least one alkene or one alkynebond, wherein the organometallic moiety comprises a Group 3 to Group 12transition metal.

Embodiment 18

The photosensitive composition of Embodiments 17, wherein the Group 3 toGroup 12 transition metal is Fe, Co, Ni, Ti, Al, Cu, Zn, Ru, Rh, Ag, Ir,Pt, Au, or Hg.

Embodiment 19

The photosensitive composition of Embodiment 17 or 18, wherein theorganometallic moiety comprises a catalyst capable of catalyzingmetathesis or cross-coupling reactions or splitting water of splittingwater.

Embodiment 20

The photosensitive composition of any one of Embodiments 17 to 19,wherein the organometallic moiety is capable of catalyzing the oxidationor reduction of an organic substrate under oxidizing or reducingconditions.

Photosensitive Composition Comprising Pendant Functional GroupsEmbodiment 21

A photosensitive composition of any one of Embodiments 1 to 20, whereinthe unsaturated organic precursor has at least one mono-, di, orpoly-functionalized cyclic or alicyclic alkene or one alkyne bond; andwherein the at least one unsaturated organic precursor comprises acompound having a structure:

wherein

Z is —O— or C(R_(a))(R_(b));

R^(P) is independently H; or C₁₋₆ alkyl optionally substituted at theterminus with —N(R_(a))(R_(b)), —O—R_(a), —C(O)O—R_(a), —OC(O)—(C₁₋₆alkyl), or —OC(O)—(C₆₋₁₀ aryl); or an optionally protected sequence of 3to 10 amino acids (preferably including R-G-D orarginine-glycine-aspartic acid);

W is independently —N(R_(a))(R_(b)), —O—R_(a), or —C(O)O—R_(a),—P(O)(OR_(a))₂, —SO₂(OR_(a)), or SO₃—;

R_(a) and R_(b) are independently H or C₁₋₆ alkyl;

the C₆₋₁₀ aryl is optionally substituted with 1, 2, 3, 4, or 5optionally protected hydroxyl groups (the protected hydroxyl groupspreferably being benzyl); and

n is independently 1, 2, 3, 4, 5, or 6.

Embodiment 22

The composition of Embodiment 21, wherein the at least one unsaturatedorganic precursor comprising a compound has a structure

where Bn is benzyl, tBu is tert-butyl, and Pbf is2,2,4,6,7-pentamethyldihydrobenzofuran.

Methods of Preparing Photosensitive Composition. Embodiment 23

A method of patterning a polymeric image on a substrate, said methodcomprising;

(a) depositing one or more layers of a photosensitive composition of anyone of Embodiments 1 to 22 on a substrate;

(b) irradiating a portion of the layer of photosensitive compositionwith a light comprising a wavelength in a range of from about 300 toabout 500 nm, preferably in a range of from about 350 to about 450 nm,so as to polymerize the irradiated portion of the layer, therebyproviding a patterned layer of polymerized and unpolymerized regions. Inother Aspects of this Embodiment, the light comprises at least onewavelength in a range of from about 300 to about 320 nm, from about 320to about 340 nm, from about 340 to about 360 nm, from about 360 to about380 nm, from about 380 to about 400 nm, from about 400 to about 420 nm,from about 420 to about 440 nm, from about 440 to about 460 nm, fromabout 460 to about 480 nm, from about 480 to about 500 nm, or acombination thereof.

Embodiment 24

The method of Embodiment 23, comprising depositing a plurality of layersof a photosensitive composition on a substrate before irradiation, atleast one of which is a photosensitive composition of any one ofEmbodiments 1 to 22.

Embodiment 25

The method of Embodiment 23 or 24, wherein the at least one layer ofphotosensitive composition is deposited by spin coating, dip coating, orspray coating.

Embodiment 26

The method of Embodiment 23 or 24, wherein photosensitive composition isa gelled, semi-solid or solid film and is deposited by laminating on thesubstrate.

Embodiment 27

The method of any one of Embodiments 23 to 26, wherein the irradiatedportion is patterned through use of a photomask, by a direct writingapplication of light, by interference, nanoimprint, or diffractiongradient lithography, by inkjet 3D printing, stereolithography,holography, or digital light projection (DLP). In certain Aspects ofthis Embodiment, the catalysts can be activated using 2- or 3-photonenergy sources at 700 to 800 nm, more specifically using a 790 nm laser.

Embodiment 28

The method of any one of Embodiments 23 to 27, wherein the light has anintensity in a range of about 1 mW/cm² to 10 W/cm², preferably about 10mW/cm² to 200 mW/cm² at at least one wavelength in the range of about250 to about 800 nm, or about from about 220 to about 440 nm.

Embodiment 29

The method of any one of Embodiments 23 to 28, wherein the patternedlayer comprises at least one feature having dimensions on the nanometeror micron scale.

Embodiment 30

The method of any one of Embodiments 23 to 29, further comprisingremoving the unpolymerized region of the pattern.

Polymerized Compositions Embodiment 31

A polymerized composition prepared according to any one of Embodiments23 to 29, or an article of manufacture comprising the polymerizecomposition.

Embodiment 32

The polymerized composition of Embodiment 31, wherein the composition isa patterned layer.

Embodiment 33

A tissue scaffold comprising a polymerized composition of claim 30 or31.

Embodiment 34

The tissue scaffold of Embodiment 33, further comprising at least onecell population.

Method of Forming 3-D Structures of Laminated PhotosensitiveCompositions, Using any Ru-Carbene Catalyst Embodiment 35

A method comprising;

(a) depositing at least two layers of a composition having at least onealkene or alkyne capable of undergoing a metathesis polymerization orcrosslinking reaction and a photoactivator admixed or dissolved therein,at least one layer comprising a composition of any one of Embodiments 1to 22, said deposition forming a stacked assembly;

(b) irradiating at least a portion of the stacked assembly with light,such that light penetrates and irradiates at least two layers of thestacked assembly, under conditions sufficient to polymerize or crosslinkat least portions of adjacent layers of the stacked assembly.

Embodiment 36

The method of Embodiment 35, wherein light passes through and irradiatesat all layers of the stacked assembly, under conditions sufficient topolymerize or crosslink at least portions of adjacent layers of thestacked assembly.

Embodiment 37

The method of Embodiment 35 or 36, wherein the irradiating is done bypatterned exposure of light to the stacked composition, so as to providea three-dimensional pattern of polymerized and unpolymerized regionsthrough the stacked assembly.

Embodiment 38

The method of Embodiment 379, wherein the irradiation is patternedthrough use of a photomask, by a direct writing application of light, byinterference, nanoimprint, or diffraction gradient lithography, byinkjet 3D printing, stereolithography, holography, or digital lightprojection (DLP).

Embodiment 39

The method of any one of Embodiments 35 to 38, wherein each layer ofcomprises a pre-formed polymer which may be the same or different fromother pre-formed polymer(s) in the other layer(s).

Embodiment 40

The method of any one of Embodiments 35 to 39, wherein the thickness ofeach layer is independently on the millimeter scale (e.g., from about 1mm to about 10 mm, from about 10 mm to about 50 mm, from about 50 mm toabout 100 mm, from about 100 mm to about 500 mm, from about 500 mm toabout 1000 mm, or a combination thereof), the micron scale (e.g., fromabout 1 micron to about 10 microns, from about 10 microns to about 50microns, from about 50 microns to about 100 microns, from about 100microns to about 500 microns, from about 500 microns to about 1000microns, or a combination thereof), or the nanometer scale (e.g., in arange of from about 50 to about 100 nm, from about 100 to about 200 nm,from about 200 to about 300 nm, from about 300 to about 400 nm, fromabout 400 to about 500 nm, from about 500 to about 600 nm, from about600 to about 700 nm, from about 700 to about 800 nm, from about 800 toabout 900 nm, from about 900 to about 1000 nm, or a combinationthereof.)

Embodiment 41

The method of any one of Embodiments 35 to 40, wherein the polymer in atleast one layer is a block copolymer.

Embodiment 42

The method of any one of Embodiments 35 to 41, wherein the polymer is atleast one layer of block copolymer, the block copolymer being adendritic (wedge) or brush (graft, bottlebrush) copolymer.

Embodiment 43

The method of any one of Embodiments 35 to 42, wherein the polymer is atleast one layer of block copolymer exhibiting domains having dimensionsin a range of from about 5 to about 1500 nanometer domains, or in arange of from about 75 to about 300 nm.

Embodiment 44

The method of any one of Embodiments 35 to 43, wherein the polymer isderived from polymerization of a polymer precursor, and whereinunreacted polymer precursor in the layer provides the at least onealkene or alkyne in the composition.

Embodiment 45

The method of any one of Embodiment 35 to 44, wherein adjacent layers ofat least two sequentially deposited layers are compositionallydifferent.

Embodiment 46

The method of any one of Embodiments 35 to 45, wherein adjacent layersof at least two sequentially deposited layers are compositionally thesame.

Embodiment 47

A stacked polymer composition prepared according to any one ofEmbodiments 35 to 46, or an article containing said stacked polymercomposition.

Embodiment 48

A photonic structure prepared according to any one of Embodiments 35 to46.

Embodiment 49

A method comprising a vat photopolymerization, wherein a photosensitivecomposition of any one of Embodiments 1 to 22 is cured directly onto atranslated or rotated substrate, and the irradiation is patterned viastereolithography, holography, or digital light projection (DLP).

EXAMPLES

The following Examples are provided to illustrate some of the conceptsdescribed within this disclosure. While each Example is considered toprovide specific individual embodiments of composition, methods ofpreparation and use, none of the Examples should be considered to limitthe more general embodiments described herein.

In the following examples, efforts have been made to ensure accuracywith respect to numbers used (e.g. amounts, temperature, etc.) but someexperimental error and deviation should be accounted for. Unlessindicated otherwise, temperature is in degrees C., pressure is at ornear atmospheric.

Example 1: Screening Experiments Comparing Ruthenium MetathesisCatalysts Comprising Phenanthroline and Bipyridine Ligands

A series of photosensitive compositions were prepared using thecatalysts generated in situ using Catalyst C627 and butyl vinyl ether(BVE), according to Table 1:

TABLE 1 Catalysts compositions prepared using 1 equivalent C627, 5equivalents Ligand, and 10 equivalents BVE in CHCl₃; final concentrationof catalyst was equivalent to 10 mg/mL of C627. Ligand 1

Ligand 2

Ligand 3

Ligand 4

After 18 hours of stirring the catalyst solutions at ca. 400 rpm,photopolymer solutions were prepared by adding 20 microliters of eachcatalysts solution to 2 mL of a dicyclopenadiene solution containingapproximately 6 wt % tricyclopentadiene. The presumed latent catalystswas the corresponding butyl vinyl carbene.

One mL of each prepared LCS resin was kept in the dark at RT for onehour, with no change in viscosity observed (FIG. 4A).

One mL of each prepared LCS resin was irradiated in vials with 1000 mJ @405 nm (14.6 mW, 68.5 sec), with corresponding changes in viscosityobserved (FIG. 4B). The latent catalyst complex formed with2,2′-bipyridine (1) displayed significantly faster photoinitiation thanthe other catalysts. It clearly gelled. The latent catalyst complexformed with 4,4′-dimethyl-2,2′-bipyridine (3) showed the initial stagesof crosslinking under these conditions. The latent catalyst complexesformed with phenanthroline (2) and 4,4′-dimethoxy-2,2′-bipyridine (4)provided no evidence of viscosity change under these conditions.

Example 2: Testing of Bathophenanthroline Chelate

A latent catalyst solution was prepared by stirring together 23.25 mgbathophenanthroline, 29.22 mg, GrubbsII-Hoveyda C627, 15 μL butyl vinylether, and 0.58 mL chloroform, as described in Example 1. After stirringfor 24 hours at room temperature, 8 μL of this latent catalyst solutionwas added to 1 mL of a dicyclopentadiene solution containingapproximately 6% tricyclopentadiene. The resulting solution representedan olefin-metathesis based photopolymer resin. A drop of this solutionwas sandwiched between two glass slides containing a 200 micron thickspacer. After an exposure of 990 mJ/cm² at λ=405 nm at 50° C., thephotopolymer liquid did not gel.

Example 3: Testing of Phenanthroline Chelate

A latent catalyst solution was prepared by stirring together 12.37 mgphenanthroline, 28.67 mg GrubbsII-Hoveyda C627, 15 μL butyl vinyl ether,and 0.57 mL chloroform. After stirring for 24 hours at room temperature,8 μL of this latent catalyst solution was added to 1 mL of adicyclopentadiene solution containing approximately 6%tricyclopentadiene. The resulting solution represents anolefin-metathesis based photopolymer resin. A drop of this solution wassandwiched between two glass slides containing a 200 micron thickspacer. After an exposure of 990 mJ/cm² at λ=405 nm at 50° C., thephotopolymer liquid did not gel.

Example 4: Testing of Other Phenanthroline Derivative Chelates

Using the procedure of Example 3, three other phenanthroline derivateswere tested for photolatency. None of these catalysts polymerized thedicyclopentadiene-based resin solutions under the conditions of thetest.

Example 5: Testing of Bipyridine Chelate

A latent catalyst solution was prepared by stirring together 20 mgbipyridine, 76 mg GrubbsII-Hoveyda C627, 38 μL butyl vinyl ether, and1.50 mL chloroform. After stirring for 24 hours at room temperature, 8μL of this latent catalyst solution was added to 1 mL of adicyclopentadenne solution containing approximately 6%tricyclopentadiene. The resulting solution represented anolefin-metathesis based photopolymer resin. A drop of this solution wassandwiched between two glass slides containing a 200 micron thickspacer. After an exposure of 990 mJ/cm² at λ=405 nm at 50° C., thephotopolymer liquid gelled.

A photopolymer ‘working curve’ was created following the procedure of P.F. Jacobs (Fundamentals of Stereolithography 1992) by measuring the curedepth of the gelled material as a function of the dosage of light. Theresults are shown in FIG. 5.

Example 6: Testing of 4,4′-Di-Tertbutyl-2,2′-bipyridine Chelate

A latent catalyst solution was prepared by stirring together 22 mg4,4′-di-tert-butyl-2,2′-bipyridine, 26 mg GrubbsII-Hoveyda C627, 13 μLbutyl vinyl ether, and 0.51 mL chloroform. After stirring for 24 hoursat room temperature, 8 μL of this latent catalyst solution was added to1 mL of a dicyclopentadiene solution containing approximately 6%tricyclopentadiene. The resulting solution represented anolefin-metathesis based photopolymer resin. A drop of this solution wassandwiched between two glass slides containing a 200 micron thickspacer. After an exposure of 990 mJ/cm² at λ=405 nm at 50° C., thephotopolymer liquid gelled.

A photopolymer ‘working curve’ was created following the procedure of P.F. Jacobs (Fundamentals of Stereolithography 1992) by measuring the curedepth of the gelled material as a function of the dosage of light. Theresults are shown in FIG. 6.

Example 7: Testing of 4,4′-Dibromo-2,2′-bipyridine Chelate

GrubbsII-Hoveyda C627 catalyst (56 mg) and 4-4′-dibromo-2-2′-bipyridine(30 mg) were weighed into a glass vial and brought into a nitrogenpurged glove box. Chloroform (1.12 mL) and 1,4-butanediol divinyl ether(28 microliters) were then added via pipette. The vial was capped,wrapped with foil to protect from ambient light and the solution stirredfor 18 hours. 0.032 mL of this solution was added to 4 mL of adicyclopentadiene solution containing approximately 6%tricyclopentadiene. A photopolymer ‘working curve’ was created using theresulting solution as described above by measuring the cure depth of thegelled material as a function of the dosage of light. The followingresults were obtained at 385 nm: Critical Exposure: 892.720 mJ/cm2,penetration depth=1.397 mm

Example 8: Testing of 4,4′-Di-tertbutyl-2,2′-bipyridine Chelate

GrubbsII-Hoveyda C627 catalyst (56 mg) and 4-4′-dimethyl-2-2′-bipyridine(17.4 mg) were weighed into a glass vial and brought into a nitrogenpurged glove box. 1.12 mL chloroform and 28 microliters of1,4-Butanediol divinyl ether were then added via pipette. The vial wascapped, wrapped with foil to protect from ambient light and the solutionstirred for 18 hours. 0.032 mL of this solution was added to 4 mL of adicyclopentadiene solution containing approximately 6%tricyclopentadiene. The resulting solution represents anolefin-metathesis based photopolymer resin. A photopolymer ‘workingcurve’ was created using the resulting solution following the proceduredescribed above by measuring the cure depth of the gelled material as afunction of the dosage of light. The following results were obtained at385 nm: Critical Exposure: 1042.445 mJ/cm², penetration depth=1.9694 mm

Example 8: Testing of Other Bipyridine Derivative Chelates

Attempts to form latent photocatalysts with four other bipyridinederivatives were surprisingly unsuccessful under the standard conditionsdescribed herein.

In the case of the 4,4′-di-methoxy-2,2′-bipyridine, under the conditionsdescribed in Examples 5-8, no measurable film was formed at exposures upto 6400 mJ/cm2 at 385 nm.

Photopolymer solutions containing the 1-(isoquinolin-1-yl)isoquinolinechelate did not form stable solutions under conditions analogous to theother substituted pyridine examples. Precipitation of the rutheniumcomplex made it difficult to quantify photopolymerization kinetics.

Example 9: Stereolithographic 3D-Printing

A PLOMP photopolymer prepared analogously to Example 3 was used in aDigital Light Projection (DLP, also referred to as Dynamic MicromirrorArray (DMD)) stereolithographic 3D printer. A rectangular bar wasprinted for heat distortion temperature analysis, by irradiating 200micron thick layers with 750 mJ/cm² of 385 nm light at a temperature of50° C. The printed bars were subsequently heated in an oven to 160° C.to ensure the polymerization went to completion. These bars were testedusing for their heat distortion temperature, as depicted in Figure ##.The following values were observed: HDT=127° C. @ 0.445 MPa, 121° C. @1.82 MPa

Example 10

U.S. patent application Ser. No. 14/505,824, filed Oct. 3, 2014, whichis incorporated by reference herein in its entirety, or at least for itsexamples, describes the use of latent Fischer-type ruthenium catalystcontaining phenanthroline. One example is reiterated here asrepresentative of the types of chemistries available with the morereactive latent ruthenium catalyst containing bipyridine ligands

A solution of 95% dicyclopentadiene and 5% ethylidene norbornene (10 mLtotal, % by volume) was added to a scintillation vial and degassed withargon. The ‘Grubbs 2’ catalyst shown above (2.1 mg) was dissolved in 100microliters of degassed chloroform, and this catalyst solution was addedto the dicyclopentadiene solution while stirring under argon. At 27.5minutes, the solution reached the desired viscosity, and thering-opening metathesis polymerization was quenched by 2.5 mg1,10-phenanthroline in 0.5 mL ethyl vinyl ether. The solution wasstirred for 5 minutes to ensure homogeneous quenching and then storedunder argon in the dark overnight before using for photolithography.This ‘parent’ photoresist could be functionalized with a wide variety ofmolecules without disrupting the PLOMP patterning process.

As those skilled in the art will appreciate, numerous modifications andvariations of the present disclosure are possible in light of theseteachings, and all such are contemplated hereby. For example, inaddition to the embodiments described herein, the present disclosurecontemplates and claims those inventions resulting from the combinationof features of the disclosure cited herein and those of the cited priorart references which complement the features of the present disclosure.Similarly, it will be appreciated that any described material, feature,or article may be used in combination with any other material, feature,or article, and such combinations are considered within the scope ofthis disclosure.

The disclosures of each patent, patent application, and publicationcited or described in this document are hereby incorporated herein byreference, each in its entirety, for all purposes.

What is claimed:
 1. A photosensitive composition comprising a rutheniumcarbene metathesis catalyst of Formula (I) or a geometric isomerthereof:

admixed within a polymerizable material matrix comprising at least oneunsaturated organic precursor; wherein X¹ and X² are independentlyanionic ligands; Y is O, N—R¹, or S; and Q is a two-atom linkage havingthe structure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably—CR¹¹R¹²_CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independentlyhydrogen, hydrocarbyl, or a substituted hydrocarbyl; R¹ and R² areindependently hydrogen, optionally substituted hydrocarbyl, or may belinked together to form an optionally substituted cyclic aliphaticgroup; R³ and R⁴ are independently optionally substituted hydrocarbyl;and R⁵ and R⁶ are independently H, C₁₋₂₄alkyl, C₁₋₂₄alkoxy,C₁₋₂₄fluoroalkyl, C₁₋₂₄fluoroalkoxy, C₁₋₂₄alkylhydroxy,C₁₋₂₄alkoxyhydroxy, C₁₋₂₄fluoroalkylhydroxy(includingperfluoroalkylhydroxy), C₁₋₂₄fluoroalkoxyhydroxy, halo, cyano, nitro, orhydroxy; and m and n are independently 1, 2, 3, or
 4. 2. Thephotosensitive composition of claim 1, wherein R¹ is H, R² is C₁₋₆alkyl, and Y is O.
 3. The photosensitive composition of claim 1, whereinQ is —CH₂—CH₂— and either R³ or R⁴, or both R³ and R⁴ are phenyl groups,optionally substituted in the 2, 6 positions with independent C₁₋₆ alkylgroups.
 4. The photosensitive composition of claim 1, wherein Q is—CH₂—CH₂— and R³ and R⁴ are independently mesityl or optionallysubstituted adamantyl.
 5. The photosensitive composition of claim 1,wherein R⁵ and R⁶ are independently H, methyl, ethyl, propyl, butyl,methoxy, trifluoromethyl, fluoro, chloro, bromo, cyano, or nitro.
 6. Thephotosensitive composition of claim 1, where the metathesis catalystcomprises a compound having a structure:


7. The photosensitive composition of claim 1, wherein R⁵ and R⁶ arepresent in the 3,3′ or 4,4′ or 5,5′ or 6,6′ position, respectively


8. The photosensitive composition of claim 1, wherein the unsaturatedorganic precursor comprises a mono-unsaturated cyclic olefin; amonocyclic diene; or a bicyclic or polycyclic olefin.
 9. Thephotosensitive composition of claim 1, wherein the unsaturated organicprecursor is a ROMP precursor.
 10. A method of patterning a polymericimage on a substrate, said method comprising; (a) depositing a layer ofa photosensitive composition of claim 1 on a substrate; (b) irradiatinga portion of the layer of photosensitive composition with a lightcomprising at least one wavelength in a range of from about 250 to about800 nm, so as to polymerize the irradiated portion of the layer, therebyproviding polymerized and unpolymerized regions in the layer.
 11. Themethod of claim 10, wherein: (a) the photosensitive composition isdeposited by spin coating, dip coating, or spray coating or whereinphotosensitive composition is a gelled, semi-solid or solid film and isdeposited by laminating on the substrate; and wherein (b) the irradiatedportion is patterned through use of a photomask, by a direct writingapplication of light, or by interference, nanoimprint, or diffractiongradient lithography, or by stereolithography, holography, or digitallight projection (DLP); and further wherein (c) the unpolymerized regionof the pattern is removed.
 12. A patterned polymer layer preparedaccording to claim 11, or an article containing said patterned polymerlayer.
 13. The photosensitive composition of claim 1, wherein theruthenium carbene metathesis catalyst is generated in situ by the mixingof an optionally substituted 2,2′-bipyridine, a quenching agent of

and a metathesis catalyst of Formula (IIA), (IIB), (IIIA), or (IIIB); ora geometric isomer thereof:

wherein: L³ and L⁴ are independently neutral electron donor ligands; kand n are independently 0 or 1; and R^(A), and R^(B) are independentlyhydrogen or optionally substituted hydrocarbyl, or may be linked to forman optionally substituted aromatic or aliphatic cyclic group.
 14. Thephotosensitive composition of claim 1 and wherein the polymerizablematerial matrix further comprises at least one organometallic moietyhaving a pendant unsaturated moiety capable of metathesizing with the atleast one unsaturated organic precursor, the pendant unsaturated moietycomprising at least one alkene or one alkyne bond, wherein theorganometallic moiety comprises a Group 3 to Group 12 transition metal.15. The photosensitive composition of claim 14, wherein the Group 3 toGroup 12 transition metal is Fe, Co, Ni, Ti, Al, Cu, Zn, Ru, Rh, Ag, Ir,Pt, Au, or Hg.
 16. The photosensitive composition of claim 1, whereinthe at least one unsaturated organic precursor comprising a compoundhaving a structure:

wherein Z is —O— or C(R_(a))(R_(b)); R^(P) is independently H; or C₁₋₆alkyl optionally substituted at the terminus with —N(R_(a))(R_(b)),—O—R_(a), —C(O)O—R_(a), —OC(O)—(C₁₋₆ alkyl), or —OC(O)—(C₆₋₁₀ aryl); oran optionally protected sequence of 3 to 10 amino acids (preferablyincluding R-G-D or arginine-glycine-aspartic acid); W is independently—N(R_(a))(R_(b)), —O—R_(a), or —C(O)O—R_(a), —P(O)(OR_(a))₂,—SO₂(OR_(a)), or SO₃—; R_(a) and R_(b) are independently H or C₁₋₆alkyl; the C₆₋₁₀ aryl is optionally substituted with 1, 2, 3, 4, or 5optionally protected hydroxyl groups; and n is independently 1, 2, 3, 4,5, or
 6. 17. The photosensitive composition of claim 16, wherein themetathesis catalyst is represented by the structure:


18. A method of patterning a polymeric image on a substrate, said methodcomprising; (a) depositing one or more layers of a photosensitivecomposition of claim 17 on a substrate; (b) irradiating a portion of thelayer of photosensitive composition with a light comprising a wavelengthin a range of from about 250 to about 800 nm, so as to polymerize theirradiated portion of the layer, thereby providing a patterned layer ofpolymerized and unpolymerized regions; and (c) removing theunpolymerized region of the pattern.
 19. A polymerized compositionprepared according to claim 18, or an article of manufacture comprisingthe polymerize composition.
 20. A method comprising a vatphotopolymerization, wherein a photosensitive composition of claim 1 iscured directly onto a translated or rotated substrate, and theirradiation is patterned via stereolithography, holography, or digitallight projection (DLP).
 21. A method comprising; (a) depositing two ormore layers of a composition having at least one alkene or alkynecapable of undergoing a metathesis polymerization or crosslinkingreaction, said deposition forming a stacked assembly; (b) irradiating atleast a portion of the stacked assembly with light, such that lightpenetrates and irradiates at least two layers of the stacked assembly,under conditions sufficient to polymerize or crosslink at least portionsof adjacent layers of the stacked assembly; wherein at least one layercomprises a photosensitive composition of claim
 1. 22. The method ofclaim 21, wherein the photosensitive composition of claim 1 comprises acatalyst represented by the structure of formula (IA):


23. The method of claim 21, wherein light passes through and irradiatesat all layers of the stacked assembly, under conditions sufficient topolymerize or crosslink at least portions of adjacent layers of thestacked assembly.
 24. The method of claim 21, wherein the irradiating isdone by patterned exposure of light to the stacked composition, thusproviding a three-dimensional pattern of polymerized and unpolymerizedregions through the stacked assembly.
 25. The method of claim 21,wherein the irradiation is patterned through use of a photomask, by adirect writing application of light, by interference, nanoimprint, ordiffraction gradient lithography, by inkjet 3D printing,stereolithography, holography, or digital light projection (DLP). 26.The method of claim 21, wherein the polymer in at least one layer is adendritic (wedge) or brush (graft, bottlebrush) block copolymer.
 27. Themethod of claim 21, wherein adjacent layers of at least two sequentiallydeposited layers are compositionally different.
 28. A stacked polymercomposition prepared according to claim 21, or an article containingsaid stacked polymer composition.
 29. A photonic structure comprising astacked polymer composition of claim 28.